CN1564708A - Ion transport membrane apparatus and process - Google Patents

Ion transport membrane apparatus and process Download PDF

Info

Publication number
CN1564708A
CN1564708A CN 02819747 CN02819747A CN1564708A CN 1564708 A CN1564708 A CN 1564708A CN 02819747 CN02819747 CN 02819747 CN 02819747 A CN02819747 A CN 02819747A CN 1564708 A CN1564708 A CN 1564708A
Authority
CN
China
Prior art keywords
oxygen
gas stream
reaction
stream
heat exchanger
Prior art date
Application number
CN 02819747
Other languages
Chinese (zh)
Inventor
T·G·哈尔沃森
V·E·贝格斯滕
P·S·阿普特
N·R·克斯卡
R·A·范斯罗滕
Original Assignee
普莱克斯技术有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to US09/925,366 priority Critical patent/US20030039601A1/en
Application filed by 普莱克斯技术有限公司 filed Critical 普莱克斯技术有限公司
Publication of CN1564708A publication Critical patent/CN1564708A/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/384Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/008Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
    • B01J8/009Membranes, e.g. feeding or removing reactants or products to or from the catalyst bed through a membrane
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0403Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal
    • B01J8/0423Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more otherwise shaped beds
    • B01J8/0426Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more otherwise shaped beds the beds being superimposed one above the other
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0446Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
    • B01J8/0449Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
    • B01J8/0453Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds the beds being superimposed one above the other
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0496Heating or cooling the reactor
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02Preparation of oxygen
    • C01B13/0229Purification or separation processes
    • C01B13/0248Physical processing only
    • C01B13/0251Physical processing only by making use of membranes
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02Preparation of oxygen
    • C01B13/0229Purification or separation processes
    • C01B13/0248Physical processing only
    • C01B13/0251Physical processing only by making use of membranes
    • C01B13/0255Physical processing only by making use of membranes characterised by the type of membrane
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00106Controlling the temperature by indirect heat exchange
    • B01J2208/00115Controlling the temperature by indirect heat exchange with heat exchange elements inside the bed of solid particles
    • B01J2208/00132Tubes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00106Controlling the temperature by indirect heat exchange
    • B01J2208/00168Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00185Fingers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00106Controlling the temperature by indirect heat exchange
    • B01J2208/00168Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00194Tubes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00477Controlling the temperature by thermal insulation means
    • B01J2208/00495Controlling the temperature by thermal insulation means using insulating materials or refractories
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/0053Controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002Chemical plants
    • B01J2219/00004Scale aspects
    • B01J2219/00006Large-scale industrial plants
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00761Details of the reactor
    • B01J2219/00763Baffles
    • B01J2219/00765Baffles attached to the reactor wall
    • B01J2219/00777Baffles attached to the reactor wall horizontal
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0205Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0205Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0244Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/025Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0261Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0283Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08Methods of heating or cooling
    • C01B2203/0805Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205Composition of the feed
    • C01B2203/1211Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235Hydrocarbons
    • C01B2203/1241Natural gas or methane
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/80Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/84Energy production
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00Purification or separation of specific gases
    • C01B2210/0043Impurity removed
    • C01B2210/0046Nitrogen

Abstract

生产合成气的反应器(72)包括四个组件:在两个低压气流(含氧气流(10)和贫氧气流(18))之间传递热量的第一热交换器;在两个高压流体气流(含碳氢化合物的反应气流(38)和合成气产品气流(40))之间传递热量的第二热交换器;混合导体陶瓷膜(80);以及催化剂床。 Production of synthesis gas reactor (72) comprises four components: a first heat exchanger heat transfer between two low pressure streams (an oxygen-containing gas stream (10) and oxygen-depleted gas stream (18)); the two high-pressure fluid the second heat exchanger heat transfer between the gas stream (hydrocarbon-containing reactive gas stream (38) and syngas product stream (40)); mixed conductor ceramic membrane (80); and a catalyst bed. 这些组件被设计成可彼此相互独立地膨胀或收缩,因此可避免引起高机械负荷和破坏材料的应力。 These components are designed independently of each other to be expanded or contracted, thus avoiding high mechanical loads and stresses caused material destruction.

Description

离子传输膜装置和方法 Apparatus and method of ion transport membrane

发明领域本发明涉及一种用于生产合成气和氢气的氧离子传输膜装置和方法。 Field of the Invention The present invention relates to an oxygen ion transport membrane device and a process for producing synthesis gas and for hydrogen. 更具体地说,本发明涉及这样的一种装置和方法,其中在具有完全独立地支撑于反应器内的集成热交换器和反应区域的反应器内,由包含氧气和碳氢化合物蒸汽的原料气流生产合成气产品气流。 More particularly, the present invention relates to an apparatus and method in which a reactor having completely independently supported within the reactor and a heat exchanger integrated in the reaction zone, the feed comprising oxygen and hydrocarbon vapors airflow production of synthesis gas product stream.

发明背景在许多商业上非常重要的制造过程中,从含氧气流中分离氧气是一个工序。 BACKGROUND OF THE INVENTION In many commercially important manufacturing process, separation of oxygen from oxygen-containing gas stream is a step. 一种分离氧气的方法是使用离子和电子导电陶瓷膜材料(有时也称为“氧离子传输膜”或者“OTM”或者“离子/混合导体膜单元”)。 A method of separating oxygen ion and electronic conductivity is to use a ceramic membrane material (also sometimes referred to as "oxygen ion transport membrane" or "OTM" or "ionic / mixed conductor membrane unit"). 通过这种不渗透其它物质的无孔陶瓷膜材料,可以选择性地传输氧离子和电子。 By non-porous ceramic membrane material that is impermeable to other substances, can be selectively transport both oxygen ions and electrons.

适合的陶瓷膜材料包括混合传导即离子和电子传导金属氧化物,以及离子传导金属氧化物与电子传导金属和金属氧化物的两相组合。 Suitable ceramic membrane material comprising mixed ionic and electronic conducting i.e., conductive metal oxide, and two metal oxides in combination with ion-conducting and electron-conducting metal oxides of the metal. 示范性的陶瓷组合物公开在US 5,342,431;5,599,383;5,648,304;5,702,999;5,712,220;5,733,435;6,214,757和JP 61-21717中。 Exemplary ceramic compositions are disclosed in US 5,342,431; 5,599,383; 5,648,304; 5,702,999; 5,712,220; 5,733,435; 6,214,757, and in JP 61-21717. 由离子和电子传导金属氧化物形成的陶瓷膜通常表现出氧选择性。 Conductive metal oxide ions and electrons formed by the ceramic films typically exhibit oxygen selectivity. “氧选择性”是指只有氧离子能够通过膜传输,而其它元素和离子则被挡在膜外面。 "Oxygen selectivity" means that only oxygen ions can be transmitted through the membrane, while other elements, and ions are kept outside the membrane. 特别有利的固体电解质陶瓷膜由无机氧化物制成,通常包括钙或钇稳定的锆或者具有莹石、黄褐针镍矿或者钙钛矿结构的类似氧化物。 Particularly advantageous solid electrolyte ceramic membranes are made from inorganic oxides, typically include calcium or yttrium-stabilized zirconium or analogous oxides having a fluorite, cinnamon needle nickel or a perovskite structure. 在US 5,733,069中描述了这种膜在气体纯化领域的应用。 Application of such a film in the field of gas purification is described in US 5,733,069.

在占优势的氧气分压下以及在约450℃-约1200℃的温度范围内,当在膜元件两侧保持一个化学电位差时,陶瓷膜材料具有传输氧离子和电子的能力。 In the prevailing partial pressure of oxygen and about 450 ℃ - capacity in the temperature range of about 1200 deg.] C when a chemical potential difference is maintained across the membrane element, the ceramic material having a film transport oxygen ions and electrons. 这种化学电位差是通过在离子传输膜两侧保持氧气分压的正比或电位梯度而形成的。 This chemical potential difference is maintained by the oxygen partial pressure is proportional to the potential gradient or both sides of the ion transport film formed. 在膜的阴极一侧,即暴露于含氧气体那一侧,氧气分压(PO2)或电位梯度保持在一个较高的数值,而在阳极一侧,进行传输氧的回收或利用。 The cathode side of the membrane, i.e., the side exposed to the oxygen-containing gas, the oxygen partial pressure (PO2) or potential gradient is maintained at a high value, while the anode side, for recycling or transport oxygen utilization. 在化学电位(氧气分压或电学电位)梯度存在下,氧离子能逆着总压梯度进行传输,即从阴极的较低总压传输至阳极的较高总压。 In the chemical potential (electric potential or oxygen partial pressure) gradient exists, oxygen ions can be transmitted against a total pressure gradient, i.e., a lower total pressure transmitted from the cathode to the anode of a higher total pressure.

在过去,氧离子传输膜(OTM)设计经历了耐久性和气体泄漏问题。 In the past, an oxygen ion transport membrane (OTM) design experience and durability of gas leakage. 例如,在经过多次加热或冷却循环后,设计成两端开口形(OBE)反应器管的膜没有不开裂的。 For example, after several heating or cooling cycle, designed to shape open at both ends (OBE) membrane reactor tubes No cracking. 由于热和组分膨胀,陶瓷膜管往往明显伸长或收缩,因此密封这样的陶瓷膜管的两端至少需要一个滑动的径向密封。 And a component due to thermal expansion, the ceramic membrane tube is often significantly expands or contracts, it is necessary at least at both ends of the ceramic membrane tube so sealing a radial sealing sliding. 在高的压差下,将气体沿该密封处的渗漏减少到最低程度易出现问题。 At high pressure, the gas leakage along the seal at minimized easy problems.

将OTM设计和高温、高压气对气热交换器结合在一起是非常有用的,可以实现热能的有效回收。 The OTM designs and high temperature, high pressure gas is very useful in conjunction with the gas for heat exchangers, heat recovery can be achieved effectively. 然而,实现起来却有极高难度。 However, there are extremely difficult to implement. 这些气对气热交换器的实际设计受到用在OTM设计里的合金性能的严重限制。 The actual design of the gas-gas heat exchanger is severely limited by the performance in the alloys OTM designs. 例如,在合成气氧化反应所要求的高反应器操作温度(800℃至1000℃)下,热交换材料保持最小强度。 For example, synthesis gas at the required high oxidation reactor operating temperature (800 deg.] C to 1000 deg.] C), minimum intensity holding the heat exchange material. 另外,为考虑承受高压,在任何热交换器设计中,这些材料的蠕变破裂性能肯定是需要考虑的因素。 Further, in consideration withstand high pressures, in any heat exchanger design, the creep rupture properties of these materials must be factors to be considered. 此外,热交换器设计应该考虑压力水平和相邻气流间的压差,以便将材料的应力降到最低。 In addition, the heat exchanger design should consider the pressure difference between the pressure level and the adjacent gas stream, so as to minimize the stress of the material. 当采用传统的壳-管设计理念时,在高温下操作的集成气对气热交换器可以在管壁上产生很大的温差。 When using the conventional shell - the tube design, integration of the gas-gas heat exchanger is operated at high temperatures can have a great temperature difference in the wall. 温度的不均匀分布可能是由于壳侧气体流动方式和速率的改变引起的。 Non-uniform temperature distribution may be due to changes in the shell side and gas flow rate caused embodiment.

生产合成气(氢气和一氧化碳的混合物)(也称合成气体)的反应器在现有技术中是已知的。 Reactor to produce synthesis gas (mixture of hydrogen and carbon monoxide) (also known as synthesis gas) are known in the prior art. 需要注明的是,合成气通常用在费—托法中以转化为液体产品,或者用作转化为甲醇的方法中,或者用作转化为二甲醚的方法中。 It needs to be indicated that the synthesis gas is typically used in Fischer - Tropsch process for conversion to liquid products, or used as a process for converting methanol, or dimethyl ether is used as the conversion method. 使用氧传输膜技术的反应器通常需要这样的设计构形,即原料气(烃一蒸汽混合物)以高压进入反应器,而空气气流(氧化剂气流)以稍高于标准大气压的压力进入反应器。 Using an oxygen transport membrane reactor technology generally require such a design configuration, i.e., the raw material gas (a hydrocarbon steam mixture) into the reactor at a high pressure, the air stream (oxidant stream) to slightly above normal atmospheric pressure into the reactor. 这种设计要求需要在用于密封膜管的密封元件两侧保持一个巨大的压差。 This design requires a great need to maintain pressure on both sides of the sealing element for sealing the film tube. 这种密封元件隔离开高压燃料气流和低压氧化剂气流。 Such a sealing element to isolate the high pressure and the low pressure fuel stream oxidant stream. 假如在操作过程中,密封元件突然失效或形成一条意想不到的泄漏通道,高压燃料将立即与含氧气体在高温下混合,形成强烈的火焰喷射。 If during operation, the sealing element failure or a sudden unexpected leakage path, the high-pressure fuel is mixed with the oxygen-containing gas immediately at a high temperature are formed, to form a strong flame spraying. 这些火焰喷射可能撞击附近的反应器部件,并严重损害它们的承压性能。 These flame spraying may strike reactor nearby components and serious damage to the compression properties thereof. 如果反应器不能承受高压、高温燃料,将会发生潜在危险的安全事故。 If the reactor can not withstand high pressure, high temperature fuel would occur potentially dangerous accidents. 因此,为了减少着火的风险和保持膜反应器的操作安全,对燃料气流和氧化剂气流进行物理分离和隔离是重要的。 Therefore, to reduce the risk of fire and maintaining safe operation of the membrane reactor, the fuel stream and oxidant stream physical separation and isolation are important.

现有技术试图通过使用内部金属膨胀接头和漂移的管板来解决热膨胀差问题。 Prior art has attempted to solve the problem by using the difference in thermal expansion inside the metal expansion joint and a drift tube sheet. 当对反应器内的热重整管的两端进行密封时,这些装置是需要的。 When both ends of the heat pipe in the reforming reactor was sealed, these devices are required. US 5,567,398教导了使用多个金属波纹管的紧凑蒸汽重整器来调节内部组件的热膨胀差。 US 5,567,398 teaches the use of a plurality of metal bellows compact steam reformer to adjust the difference in thermal expansion of the internal components. US 5,567,933描述了另一种蒸汽重整反应器,其特别是采用了过程原料气和产品气之间的对流热交换。 US 5,567,933 describes another steam reforming reactor, which uses a particular convective heat between the process feed gas and product gas exchange. 这种热交换器管板使用单个的金属波纹管来调节热膨胀差。 Such heat exchanger tube sheet using a single metal bellows to adjust the difference in thermal expansion. 然而,当在高温下操作时,能够充分调节轴向运动的金属波纹管经常由于疲劳和蠕变而过早地失效。 However, when operating at high temperatures, can be sufficiently adjusting the axial movement of the metallic bellows often due to fatigue and creep and fail prematurely.

合成气中含有高百分比的一氧化碳,一氧化碳可以在约400℃至约700℃的温度范围内攻击某些金属合金,这就是所谓的金属粉尘化现象。 Synthesis gas contains a high percentage of carbon monoxide which can attack certain metal alloys in the temperature range of about 400 deg.] C to about 700 deg.] C, which is a so-called metal dusting phenomenon. 这个问题在冷却含有高含量一氧化碳的合成气过程中显得尤为突出。 This problem syngas cooling process containing high levels of carbon monoxide is particularly prominent. 金属粉尘化是一种灾害性的合金碳化过程,其形成内部碳化物,在相当短的时间内使金属结构出现凹陷并变薄。 Metal dusting is a process disaster alloy carbide which is formed inside a carbide, the metal structure in a relatively short period of time and appeared thin recess. 为了避免金属粉尘化,需要保持金属表面例如热交换器壁在临界温度范围外,例如可以在壁的一侧使用沸水,用水淬灭从而冷却合成气产品气流,因此在临界温度范围内不需要热交换器,或者使用一种抗金属粉尘化的金属。 In order to avoid metal dusting, metal surfaces such as heat exchangers need to maintain the outer wall temperature of the critical range, for example, boiling water on one side of the wall, quenched with water to cool the syngas product stream, so no heat within the critical temperature range switch, or the use of an anti-metal metal dusting. 已知的对金属粉尘化有较强抗性的合金是HAYNES230合金,是一种镍-铬-钨-钼合金。 Strong metal dusting resistant alloy is known HAYNES230 alloy is a nickel - chromium - tungsten - molybdenum alloy. 然而,这种特殊的抗性合金非常昂贵,大幅度增加了反应器的成本。 However, such special resistant alloys are very expensive, significantly increases the cost of the reactor. 如果能用一种保护气体阻止合成气与OTM管板接触,那么OTM管板可以用较为便宜的合金(例如INCOLOY800 HT合金),并且反应器的综合成本也会下降。 If a protective gas can be prevented and the synthesis gas in contact OTM tubesheet, the OTM tubesheet may be cheaper alloys (e.g. INCOLOY800 HT alloy), and the overall cost of the reactor will be lowered.

其它需要考虑的是:在热交换器的进料一侧避免固体单体碳的形成。 Other considerations are: to avoid the formation of solid carbon in the monomer feed side of the heat exchanger. 根据气体组成,特别是比甲烷重的碳氢化合物的存在下,热交换器中的临界温度应该不要高于500℃至750℃。 The gas composition, in particular a weight ratio of methane in the presence of hydrocarbons, the critical temperature in the heat exchanger should be no higher than 500 deg.] C to 750 ℃. 在允许范围内升高温度,一种可能的途径是在适中温度使用一个预重整装置。 Raising the temperature within the allowable range, one possible approach is to use a pre-reformer at a moderate temperature. 现有技术中涉及用离子传输膜生产合成气的参考文献是:US 5,865,878,其在一个集成的气体涡轮循环中使用一种生产合成气的OTM膜,并且对使用的温度范围,它给出了一般的指导,其使用产品淬灭或者废热锅炉来冷却合成气产品;US 6,048,472提到了预重整装置;以及EP 0 882 670A1,它提供了用氧气传输膜生产合成气的一般论文,包括上面提到的问题。 The prior art relates to the production of synthesis gas by membrane ion transport references are: US 5,865,878, which is used for producing synthesis gas OTM membrane in an integrated gas turbine cycle and temperature range used, which gives general guidance, using a quenched product or waste heat boiler to cool the syngas product; US 6,048,472 refers to the pre-reformer; and EP 0 882 670A1, which provides a general paper film producing synthesis gas with an oxygen transmission, including the above mentioned to the problem.

通常,高温、高压气对气热交换器也使用内部绝热以保持反应器壁的温度足够低,以满足材料强度的要求。 Typically, high temperature, high pressure gas-gas heat exchanger for use internal insulation to maintain the reactor wall temperatures low enough to meet the strength of the material. 这种绝热的热交换器的整体物理尺寸和重量减损了设计紧凑集成的反应体系的能力。 Overall physical size and weight of the heat exchanger of this detracts from the ability to adiabatic compact integrated reaction system. 通常,在约800℃至约1100℃的温度水平下,操作全金属体系是不可能的,而该温度范围是制备合成气或对其进行氧化所需要的。 Typically, at a temperature level of about 800 to about 1100 ℃ deg.] C, the all-metal system operation is not possible, and the production of synthesis gas temperature range is subjected to an oxidation or required.

或者,陶瓷结构已经用于热交换表面。 Alternatively, the ceramic structure has a heat exchange surface. US 5,775,414介绍了一种用于高温、高压空气对空气的热交换器的设计,它包括陶瓷管、园顶型陶瓷管板和外部安装弹簧的膨胀装置。 US 5,775,414 describes an apparatus for expanding a high temperature high pressure air to air heat exchanger designed for, which comprises a ceramic tube, ceramic dome and the outer mounting tube plate spring. US 5,599,383描述了一种多管混合导体陶瓷膜反应器。 US 5,599,383 describes a multi-tube reactor mixed conductor ceramic membrane. 它采用两端开放管(OBE),并在两端使用气体歧管装置。 It uses an open tube ends (OBE), and using the gas manifold means at both ends. 这些陶瓷组分带来了额外的密封和歧管装置问题。 These ceramic component brings additional sealing and manifolding problems.

单独地,热交换器技术已经公开了在反应器中结合使用热交换器管和催化剂床。 Separately, the heat exchanger art has disclosed the use of a heat exchanger tube and the catalyst bed is incorporated in the reactor. US 4,405,562公开了将内部热交换器集成在催化剂床中的装置。 US 4,405,562 discloses a device for the internal heat exchanger is integrated in the catalyst bed. 流经催化剂床发生在两个轴向段中,每段都是径向流动构型。 Through the catalyst bed occurs in two axial sections each are radial flow configuration. US 5,190,731介绍了一种平衡催化剂床内温差的装置,以承受放热反应,例如合成氨反应。 US 5,190,731 describes a balance device within the catalyst bed temperature difference in order to withstand the exothermic reaction, such as ammonia synthesis. 催化剂床由散布在冷却管内的催化剂颗粒组成。 A catalyst bed of catalyst particles dispersed in the composition of the cooling pipe. 催化剂床内的气流径向穿过管到达中心管道。 Air flow radially through the catalyst bed within the tube to the center of the pipe. 然而,这些文献中没有一个提到在合成气生产过程中,催化剂床和OTM可以系统结合在一起使用。 However, these documents do not mention a synthesis gas production process, the catalyst bed may be bonded together and OTM system.

因此,需要一种用在生产合成气的反应器中的OTM系统,其不使用金属膨胀接头,并可以以这样的方式设计,即内部组件能够彼此相互独立地自由膨胀或收缩,因此避免产生高机械负荷和破坏材料的应力。 Thus, OTM reactor system in the production of synthesis gas with a need, without using the metal expansion joints, and may be designed in such a way that the internal components can be free to independently expand or contract with each other, thus avoiding high mechanical load stresses and material damage. 正如下面将讨论的,本发明提供了一种解决这种需要的方法,并且结合了其他有利的创造性特点。 As will be discussed below, the present invention provides a solution to this need, and advantageously combined with other inventive features.

发明概述本发明提供了一种生产合成气的装置,其包括一种反应器。 SUMMARY The present invention provides an apparatus for producing synthesis gas, which comprises one reactor. 位于反应器一端的第一热交换器,通过与贫氧气流的间接热交换来加热预热的含氧气流。 Heat exchanger located in the first end of the reactor, heated oxygen containing gas stream is preheated by indirect heat exchange with oxygen-depleted gas stream. 位于反应器另一端的第二热交换器,通过与合成气产品气流的间接热交换来加热包含至少一种碳氢化合物和蒸汽的反应气流。 The second heat exchanger is located at the other end of the reactor to heat the reaction gas stream comprising at least one hydrocarbon and steam by indirect heat exchange with the synthesis gas product stream. 位于反应器的反应区域内的若干氧气传输膜,把氧气从含氧气流中分离出来,因此在氧气传输膜的阳极一侧产生渗透氧。 Some oxygen transport membrane located in the reaction zone of the reactor, the oxygen is separated from the oxygen-containing gas stream, thus producing permeate oxygen at the anode side of the oxygen transport membrane. 氧气传输膜的阴极一侧与第一热交换器连通,以接收含氧气流。 The cathode side of oxygen transport membrane in communication with the first heat exchanger to receive oxygen-containing gas stream. 反应区域与第二热交换器连接,以便使反应气流进入反应区域内的氧气传输膜的阳极一侧。 The reaction zone and a second heat exchanger is connected to the reaction gas flow into the anode side of the oxygen transport membrane in the reaction zone. 催化剂床位于反应区域内,促进组合的部分氧化重整水煤气转换反应中渗透氧的反应,产生合成气产品气流。 Partial oxidation catalyst bed in the reaction zone, promoting composition reforming water gas shift reaction permeate oxygen reaction to produce a synthesis gas product stream. 与第一热交换器连接的第一进入排出通道,以及与第二热交换器连接的第二进入排出通道,各自是含氧气流和贫氧气流以及反应气流和合成气产品气流进出反应器的通道。 Enters the first heat exchanger is connected with a first discharge passage, and a second inlet connected to the discharge passage of the second heat exchanger, are each an oxygen-containing gas stream and the oxygen-depleted gas stream and a reaction product gas stream and the syngas stream into and out of the reactor aisle. 第一热交换器、第二热交换器、氧气传输膜彼此相互独立地安装在反应器内,以便每个能独立地膨胀和收缩。 The first heat exchanger, a second heat exchanger, the oxygen transport membrane mounted independently one another within the reactor, so that each can independently expand and contract.

在本发明这方面,通过在设计中加入蜂窝式或伸缩式OTM和热交换器,其允许相对自由地移动,可以取消所有膜反应器中的内部金属膨胀接头。 In this aspect of the invention, by the addition of a cellular or telescopic OTM and heat exchanger design, which allows relatively free to move, cancel all internal metal membrane reactor expansion joint. 例如,采用密闭末端管的OTM合成气反应器可以这样设计:内部组件能彼此相互独立地自由膨胀或收缩。 For example, using a sealed end of the tube OTM syngas reactor can be designed: the internal components to freely expand or contract independently of each other. 这种方法防止了在操作过程中高机械负荷和破坏材料的应力的产生。 This method prevents the occurrence of high mechanical stress and damage to the material loading during operation.

此外,两个内部集成的热交换器可以与合成气/膜反应器一起包括在一个常压容器壳内。 In addition, two internal integrated heat exchanger may comprise a shell in a pressure vessel together with the synthesis gas / membrane reactor. 通过确定流体气流的相对位置,可以用低成本机械设计方法来制造它们。 By determining the relative position of the fluid stream, can be manufactured at low cost mechanical design method thereof. 采用这种设计,一个热交换器在两种具有小压力差的高压流动气流之间(工艺原料气和产品合成气)传递热量。 With this design, having a heat exchanger (process feed and product synthesis gas) heat transfer between the high pressure flow stream in both the small pressure difference. 另一个热交换器在两个有着小压力差的低压流动气流之间(原料空气和贫氧空气)传递热量。 Another heat exchanger (feed air and oxygen-depleted air) between the two transfer heat with a small pressure difference between the low pressure flow stream. 在这两种情况中,由于相邻气流间的操作压力差很小,热交换器的内部组件不会受到高应力。 In both cases, since the operation of the pressure difference is small between the adjacent gas flow, the internal components of the heat exchanger is not subjected to high stress. 薄管壁和制成的薄片材料都能用来制造这种热交换器。 And a thin wall sheet material can be used to fabricate such a heat exchanger.

有利地是,在反应物区域内设有挡板,用来形成流经反应区域和催化床的反应气流,按:轴向流动、交叉流动、轴向横向混合流动、螺旋流动、径向分段交叉流动、横向分段交叉流动的方式之一进行流动。 Advantageously, a baffle plate in the region of the reactants, the reaction for forming the gas flow through the reaction zone and the catalyst bed, by: axial flow, cross flow, transverse axial mixed flow, spiral flow, radial sections cross-flow, cross-flow, one lateral segment of the flow way. 在交叉流设置中,反应区域可以具有多孔罩管,其围绕在管状结构的氧气传输膜的周围。 In cross-flow arrangement, the reaction zone may have a porous cover tube surrounding the oxygen transport membrane tubular structure. 使用交叉流设置必须带有罩管,以避免催化剂床的过多轴向旁通,其由大部分工艺侧流经多孔罩管和混合传导膜管之间的环面形成。 Cross-flow must be provided with a shroud pipe, to avoid excessive axial bypass the catalyst bed, which is conducted from the tube and flows through the porous cover most of the mixing process between the annulus side of the film tube. 此外,罩管能阻止膜表面与催化剂之间的接触,使得能够独立地卸载和安装膜管和催化剂。 In addition, the cover tube can prevent the contact between the catalyst and the membrane surface, and so can be independently mounted membrane tubes and unload the catalyst.

氧气传输膜可以是氧气传输膜管。 An oxygen transport membrane may be an oxygen transport membrane tubes. 在反应区域和氧气传输膜管的开口端的密封处之间有一个惰性缓冲气体区域,允许非反应性气体进入,那里的压力比反应区域的压力高,从而阻止反应气体从反应气流渗入到含氧气流中。 Between the seal at the open end of the reaction zone and the oxygen transmission membrane tubes have an inert buffer gas region, to allow non-reactive gas to enter, where the pressure is higher than the pressure in the reaction zone, thereby preventing the reaction gas infiltration from the reaction gas stream to the oxygen-containing gas stream.

优选地,第一、第二热交换器都有一个与反应器相连的热交换管板,以及若干与所述管板相连的管道,它们分别是所述合成气产品气流和所述的含氧气流的内部通道。 Preferably, the first, the second heat exchanger has a heat exchange tube plate and connected to the reactor, and a plurality of pipes connected to the tube plate, which are oxygen-containing gas stream and the syngas product of internal flow passage. 如下面的讨论,每个热交换器是一个气对气热交换器,并且还包括制成壳侧隔离器板的薄壁金属板和流动通道。 As discussed below, each of the heat exchanger is an air to air heat exchanger, and further comprising a shell-side separator plate is made of a thin metal plate and the flow channel. 管板对面的热交换器末端与来自反应区域的流体气流相连,它们具有类似的压力水平:含碳氢化合物的工艺气流(阳极一侧)的压力高,含氧气流(阴极一侧)的压力低。 The opposite end of the heat exchanger tube sheet is connected to the fluid stream from the reaction zone, they have similar pressure level: high pressure hydrocarbon-containing process stream (anode side), the pressure of the oxygen-containing gas stream (cathode side) low. 管道把第一、第二热交换器分为相对的两侧,一侧为含氧原料气和贫氧气,另一侧为原料气和产品气。 The first conduit, a second heat exchanger into opposite sides, one side of the oxygen-containing feed gas and oxygen-depleted, as the other side of the feed and product gas. 第二热交换器是这样的设计,其使得在所述原料气一侧的质量速度比在所述产品气一侧的要高。 A second heat exchanger is designed so that the gas mass velocity is higher than a side of the feed gas to the product side. 在原料气一侧就产生了更高的膜系数,以这种方式,管壁温度就能保持在低于发生金属粉尘化的温度。 In the gas feed side of the membrane produces a higher coefficient, in this manner, the wall temperature can be maintained at a temperature below metal dusting occurs.

氧气传输膜可以是管状结构,有相对的封闭和开放的端口,在封闭端受到位于热交换器管板之间的支撑管板的支撑。 An oxygen transport membrane can be a tubular structure having opposed open and closed port in the closed end of the support tube is supported between the plate heat exchanger tubesheet. 结果,热交换器和氧气传输膜管通过管板附件独立地支撑在反应器壁上。 As a result, the heat exchanger tubes and the oxygen transmission through the film supported independently of the tube plate attachment on the reactor walls.

第二热交换器有第一、第二段,在位于两段之间有一个催化预重整区域。 A second heat exchanger a first, a second section, located between the two sections has a catalytic pre-reforming zone. 预重整区域包含一种预重整催化剂,在那里,它把含一个碳分子以上的碳氢化合物重整生成氢气和一氧化碳。 Pre-reforming zone comprises one pre-reforming catalyst, where it is the carbon molecule containing one or more reforming a hydrocarbon to produce hydrogen and carbon monoxide. 这有助于避免在重整区域的入口处和第二热交换器的高温端的进料侧内,在更高温度下形成单体碳。 This helps to avoid the high-temperature side in the feed at the inlet end of the reforming zone and a second heat exchanger, free carbon is formed at higher temperatures.

反应区域可以是无催化剂的区域,在这里所述的反应气流进入反应区域以促进氧化反应超过重整反应。 The reaction zone can be catalyst-free region, where the reaction gas stream entering the reaction zone to promote the oxidation reaction over reforming reaction. 这有助于迅速加热反应气流和氧气传输膜管中的反应气体。 This helps to rapidly heat the reaction the reaction gas stream and an oxygen transport membrane tubes. 另外,催化剂床还可以有一个无氧气传输膜的区域,以限定一个催化均衡区域。 Further, the catalyst bed may also be a region free of oxygen transport membrane to define a balanced catalytic region. 在这样的一个区域内,在没有氧气渗入的情况下,反应气流进行重整反应。 In such a zone, infiltrating in the absence of oxygen, the reaction gas stream reforming reaction. 这可以使离开反应区域内的工艺气体成分之间的平衡得到改善。 This can make the process gas leaving the balance between the components in the reaction zone is improved.

优选地,每个氧气传输陶瓷膜可以是管状结构,以及位于其阳极一侧的多孔载体层和位于阴极一侧的相邻密实膜构成的复合结构。 Preferably, each oxygen transport membrane may be a ceramic tubular structure, and a composite dense membrane structure adjacent the porous carrier layer which is located on the anode side and the cathode side thereof. 所述催化剂床的重整催化剂至少位于所述多孔载体的外围部分。 The catalyst bed of the reforming catalyst on at least a peripheral portion of the porous support.

任选地,反应器可以配置一个外夹套,用来预热含氧气流。 Optionally, the reaction may be configured an external jacket, to preheat the oxygen-containing gas stream. 含氧气流预热以后,可以在连接外夹套和第一热交换器之间的通道内流动。 After preheating the oxygen-containing gas stream, the flow in the channel may be connected between the outer jacket and the first heat exchanger.

另一方面,本发明提供了一种生产合成气的方法。 Another aspect, the present invention provides a process for production of synthesis gas. 在这种方法中,含氧气体被压缩到约1.5巴至约4巴(适中的压力)的压力范围内,此后,将其加热到约300℃-约600℃的过渡温度范围内。 In this method, the oxygen-containing gas is compressed to about 1.5 bar to about 4 bar (medium pressure) of the pressure range, after which it was heated to about 300 ℃ - transition within the temperature range of about 600 deg.] C. 将包含至少一种碳氢化合物和蒸汽的反应气流加热至200℃以上。 The reaction gas stream comprising at least one hydrocarbon and steam is heated to above 200 ℃. 加热后的含氧气流,导入位于反应器内的第一热交换器中,通过与贫氧气流的间接热交换来加热含氧气流。 The heated oxygen-containing gas introduced into the first heat exchanger located within the reactor vessel, the oxygen-containing gas stream is heated by indirect heat exchange with oxygen-depleted gas stream. 此后,含氧气流进入位于反应器的反应区域内的若干氧气传输膜的阴极一侧,把氧气从含氧气流中分离出来。 Thereafter, a plurality of oxygen-containing gas stream into the cathode side of oxygen transport membrane located within the reaction zone of the reactor, the oxygen is separated from the oxygen-containing gas stream. 这样的分离使得在氧气传输膜的阳极一侧产生了渗透氧。 Such separation such that a permeate oxygen on the anode side of the oxygen transport membrane. 反应气流进入位于反应器内的第二热交换器中,通过与合成气产品气流进行间接热交换,把反应气流加热到约500℃至750℃的温度范围内。 The reaction gas flow into the second heat exchanger located within the reactor by indirect heat exchange with the synthesis gas product stream, the gas stream is heated to reaction temperature in the range from about 500 deg.] C to 750 deg.] C of. 反应气流进入位于氧气传输膜阳极一侧和反应区域内的催化剂床中,促进渗透氧的反应并结合部分氧化-重整-水煤气转换反应,以生产合成气产品气流。 The reaction gas flow into the reaction oxygen transmission film located in the side of the anode catalyst bed and reaction zone to promote the penetration of oxygen and partial oxidation binding - reforming - water gas shift reaction to produce a synthesis gas product stream. 通过与反应气流进行间接热交换,对合成气产品气流进行冷却,然后从反应器中回收合成气产品气流。 , The product synthesis gas stream is cooled by indirect heat exchange with the reaction gas stream, and recovering the synthesis gas product stream from the reactor. 通过与含氧气流进行间接热交换,对贫氧气体进行冷却,然后将贫氧气体从反应器中排出。 , Of oxygen-depleted gas is cooled by indirect heat exchange with oxygen-containing gas stream, and the oxygen-depleted gas discharged from the reactor.

本发明方法使用包含所有高温操作的设备,包括在单壳内的贫氧气体与含氧气体的热交换器,合成气产品与反应原料气的热交换器,以及OTM膜反应器,从而降低本装置末端的温度,避免附加的高温工艺设备配件。 The method of the present invention comprises the use of high temperature operation of all equipment, including single-shell heat exchanger with oxygen-depleted oxygen-containing gas, syngas product and the reaction raw material gas heat exchanger, and OTM membrane reactor, thereby reducing the present the temperature of the end of the apparatus, avoiding additional high temperature process equipment parts. 通过相似压力水平气流之间的热交换,热交换器的设计和构造变得相当容易。 In a similar level of heat exchange between the air flow pressure, the design and construction of the heat exchanger becomes relatively easy.

优选地,反应气流的反应气体在反应区域和催化剂床内,按轴向流动、轴向横向混合流动、螺旋流动、径向分段交叉流动、横向分段交叉流动之一的方式进行流动。 Preferably, the reaction gas stream in the reaction zone and the catalyst bed, in axial flow, mixed flow axial lateral, spiral flow, radial flow cross sections, the transverse cross-sections, one embodiment of the flow flows. 有利地是,至少可以调节反应气体的组成、透过氧气传输膜管的渗透氧的氧气渗透速率、位于反应区域内的可促进反应气流和渗透氧气反应的催化剂活性三者之一,使吸热重整反应的热量与放热氧化和水煤气转换反应的热量达到局部平衡,以保持OTM表面在理想的操作温度范围内,通常为800℃到1100℃之间。 Advantageously, the at least adjusting the composition of the reaction gas, an oxygen permeation rate of oxygen permeation through the oxygen transport membrane tubes, positioned one reactant gas stream and may facilitate penetration of the active oxygen reaction catalyst in the reaction zone three, endothermic heat converting exothermic heat of the oxidation reaction and the water gas reforming reaction reaches equilibrium partial, OTM surface to maintain within the desired operating temperature range is generally between 800 deg.] C to 1100 ℃. 这有利于避免氧气传输膜管过热。 This helps to avoid overheating of the oxygen transport membrane tubes.

缓冲气体区可以位于第一热交换器和反应区域之间。 Gas buffer region may be located between the heat exchanger and the first reaction zone. 在稍高于反应气流压力条件下,将非反应性气体导入缓冲气体区,以避免反应气体从反应气流渗入到含氧气流中。 In the stream slightly above the reaction pressure conditions, the non-reactive gas introduced into the gas buffer zone to avoid infiltration of reactant gas into the oxygen-containing gas stream from the reaction gas stream.

合成气产品气流从所述的产品第二热交换器排放的温度优选在700℃以上,以抑制那里的金属粉尘化,反应器外的产品合成气气流在外部热交换器内用沸腾的水进一步冷却至约400℃以下,以抑制外部热交换器内的金属粉尘化。 Syngas product stream from the second heat exchanger the temperature of the discharged product is preferably above 700 deg.] C, where the metal to inhibit dusting, product synthesis gas stream outside the reactor within the external heat exchanger further with boiling water cooled to about 400 ℃, to inhibit metal dusting in the outer heat exchanger. 或者,在从反应区域出来后,液态水可以注入产品合成气气流中,通过淬灭可以部分冷却产品合成气气流,从而抑制第二热交换器内的金属粉尘化。 Alternatively, after the reaction zone from the liquid water can be injected into the syngas product stream by quenching the product may be partially cooled synthesis gas stream, thereby inhibiting metal dusting in the second heat exchanger. 优选地是,当含氧气体气流和反应气体气流进入反应区域时,它们具有约200℃以上的温差。 Preferably, when the oxygen-containing gas stream and the reaction gas stream into the reaction zone, they have a temperature difference of above about 200 ℃.

在另一种配置中,可以在开始时将第二热交换器内的反应气流加热到约500℃。 In another arrangement, the reactive gas stream within the second heat exchanger may be heated to about 500 deg.] C at the start. 然后反应气流流经第二热交换器内的催化预重整区域,其中具有一个以上碳分子的碳氢化合物被重整为氢气和一氧化碳,以抑制在更高温度下形成单体碳,然后加热到约700℃以上。 The reaction was then catalytic pre-reforming region in the gas flow through the second heat exchanger, wherein a hydrocarbon having more carbon molecule is reformed to hydrogen and carbon monoxide, to inhibit the formation of free carbon at higher temperatures, followed by heating above about 700 ℃. 反应气体在进入所述催化剂床之前与渗透进来的氧气进行部分氧化反应。 The reaction gas coming in the partial oxidation reaction with the oxygen permeability before entering the catalyst bed. 经过反应区域后,在没有氧气渗入的情况下,反应气体在均衡区域内可进行重整反应。 After the reaction zone, in the absence of oxygen into the case, the reaction gas in the reforming reaction zone may equalization.

有利地是,一开始将起始空气流导入反应器中,并且把燃料注入到离开反应区域阴极一侧的气流中,与氧气在起始空气流中进行反应。 Advantageously, a start start air flow introduced into the reactor, and the fuel is injected into the gas stream leaving the reaction zone of the cathode side, the air flow in the initial reaction with oxygen. 这样提高了气流的温度,通过间接的热传递,入口空气的温度加热了OTM管。 This increases the temperature of the gas stream through indirect heat transfer, the temperature of the heated air inlet tube OTM. 持续注入所述燃料直到氧气传输膜管到达操作温度,到那时,再将反应气流导入到第二热交换器中。 Continuing injection of the fuel until the oxygen transport membrane tube to operating temperature, time, and the reaction gas flow introduced into the second heat exchanger.

附图的简要描述尽管说明书和权利要求书已经清楚地指出了被申请人视作本发明的主题,但是结合下面这些附图,本发明能够更好地得到理解,其中:图1为根据本发明的方法生产合成气的示意图,在该方法中使用将集成热交换器和氧气传输膜反应器-分离器结合在一起的装置;图2为图1中所示装置的剖视图;图3为螺旋型流动的催化剂床的剖视图;图4为径向分段交叉流动的催化剂床的剖视图;图5为横向分段交叉流动的催化剂床的剖视图;图6为催化剂床内不同管长度的氧气传输膜管的立体图;图7为管板装置的剖视图,用来支撑图1所示装置中的氧离子传输膜管;图8为图1装置中的催化剂床装置的剖视图;图9为图1装置中使用的第一热交换器的剖视图;图10为图1的水平剖视图;图11为图1所示装置的缓冲气体封闭结构的详细剖视图;图12为图2装置的下半部 BRIEF DESCRIPTION OF THE DRAWINGS While the specification and claims have clearly pointed out the subject matter regarded as the invention Applicants, but the combination of these drawings the following, the present invention can be better understood, in which: FIG 1 according to the present invention the schematic process for producing synthesis gas, used in the method to integrate the heat exchanger and the oxygen transport membrane reactor - separator means joined together; FIG. 2 is a cross-sectional view of the device shown in FIG. 1; FIG. 3 is a spiral a cross-sectional view of the catalyst bed flow; FIG. 4 is a radial sectional view of a cross-flow catalyst bed segment; FIG. 5 is a cross-sectional view of a cross catalyst bed flowing transverse sections; FIG. 6 is a oxygen transmission of different length of the tube within the catalyst bed membrane tube perspective view; FIG. 7 is a cross-sectional view of the tube plate means for supporting the oxygen ion transport means the film tube shown in FIG. 1; FIG. 8 is a cross-sectional view of the catalyst bed means the apparatus of figure 1; figure 9 is an apparatus used in the drawings a first cross-sectional view of the heat exchanger; FIG. 10 is a horizontal cross-sectional view of FIG. 1; FIG. 11 is a detailed sectional view of the buffer gas of the closure structure shown in FIG. 1; FIG. 12 is a lower half of the apparatus of FIG. 2 的另一结构,其带有一个预热含氧气流的外夹套。 Another configuration, a preheated oxygen-containing gas stream which has an outer jacket.

发明详述图1为使用本发明的集成装置1生产合成气的示意图。 DETAILED DESCRIPTION FIG. 1 using an integrated device of the invention according to the present invention, a schematic view of a synthesis gas production. 由空气或其它含氧气体组成的含氧气流10由压缩器12压缩到1.5巴至4巴的适中压力。 An oxygen-containing gas stream from the air or other oxygen-containing gas composition 10 is compressed by the compressor 12 to the moderate pressure of 1.5 bar to 4 bar. 然后,含氧气流10在外部热交换器16内,逆着贫氧气流18,加热到一个约200℃至约500℃的适中温度。 Then, the oxygen-containing gas stream 10 in the exterior heat exchanger 16, against the oxygen-depleted gas stream 18 is heated to a moderate temperature of about 500 to about 200 ℃ deg.] C of. 此后,将含氧气流10导入装置1,含氧气流10被贫氧气流18在第一热交换器20内以逆流的方式进一步加热到700℃以上,优选地,在第一热交换器20的暖端,至少在贫氧气流温度的150℃范围内。 Thereafter, the oxygen-containing gas stream 10 introduced into the apparatus 1, the oxygen-containing gas stream 10 is oxygen-depleted gas stream 18 in a countercurrent manner in 20 the first heat exchanger is further heated to above 700 deg.] C, preferably, in the first heat exchanger 20 warm end, at least in the range of 150 deg.] C in the oxygen-depleted gas stream temperature. 如果需要升高含氧气流10的温度,任选的燃料气流22可以导入装置1中以与贫氧气流18中的残留氧气反应并且通过任选添加的空气气流24来添加氧气。 If elevated temperatures are oxygen containing gas stream 10, fuel gas stream 22 optionally can be introduced in the reaction apparatus 1 to residual oxygen in the oxygen-depleted gas stream 18 and 24 and optionally by the addition of oxygen to the air stream to add.

然后,含氧气流10进入反应区域26中,并到达氧气传输膜管的阴极27一侧,其将在下文作更详细的讨论。 Then, the oxygen-containing gas stream 10 enters reaction zone 26, and the cathode oxygen transport membrane tube 27 side, which will be discussed in more detail below. 在氧气传输膜管内,氧气分子离解,以氧离子的形式传输通过氧气传输膜管,与来自气流38的部分反应物在阳极29处进行反应,产生氧化反应产品,然后与位于催化剂床28内且在氧化传输膜管的阳极29一侧的反应物进行反应。 Within the oxygen transport membrane tubes, the oxygen molecule dissociation, transmitted in the form of oxygen ions, oxygen transmission through the film tube, the reaction at the anode 29 and the portion of the reaction product from the gas stream 38, the oxidation reaction product, and then located within the 28 catalyst bed and anodic oxidation reaction in the reactant transport membrane tube 29 side. 其中催化剂床28也位于反应区域26内。 Wherein the catalyst bed 28 is also located within the reaction zone 26.

包含一种或多种碳氢化合物的碳氢化合物源,例如天然气,作为具有约10巴至40巴之间的压力范围的天然气体气流30,可以导入预处理区域31,该区域可能由脱硫系统组成,在用其他废热资源预加热以后,以去除有害的硫化合物。 Hydrocarbon source containing one or more hydrocarbons, such as natural gas, natural gas as a stream 30 having a pressure range of between about 10 bar to 40 bar, can be introduced into the pretreatment region 31, the region may be provided by desulfurization system composition, waste heat from other resources after pre-heating, to remove unwanted sulfur compounds. 然后,天然气气流30优选与由氢气、一氧化碳、二氧化碳及未反应的甲烷组成的循环气流32混合。 Then, a natural gas stream from the recycle stream 30 is preferably hydrogen, carbon monoxide, carbon dioxide, and unreacted methane composition 32 mixed. 如果不使用循环气流,所得合并气流34或天然气气流30进一步和蒸汽36合并以形成反应气流38。 If no recycle stream, the resulting combined gas stream 34 or gas stream 30 is further combined steam and 36 to form a reaction gas stream 38. 循环气流可以包括循环的合成气产品和来自下游反应的废气。 Recycle gas stream may include syngas product and circulating the exhaust gas from a downstream reaction. 反应气流38进入装置1后,依据其组成,在第二热交换器39内被加热到一个适中的特定温度,为约500℃至750℃范围内可避免生成单体碳的最高允许程度。 After the reaction stream 38 enters apparatus 1, based on the composition, is heated to a moderate temperature in particular the second heat exchanger 39, is in the range of from about 500 deg.] C to 750 deg.] C can be avoided to allow the highest degree of free carbon generated.

在装置1的反应区域26内,反应气流38通过与渗透氧的氧化反应被迅速加热到约800℃至约1050℃的优选温度范围内,反应气流38的成分和渗透氧参与组合的部分氧化-重整-水煤气体转换反应,生成合成气产品气流40。 In the reaction region of the device 1 26, reactive gas stream 38 oxidation reaction with permeating oxygen is rapidly heated to a preferred temperature range from about 800 deg.] C to about 1050 deg.] C, the reactant gas stream components and the permeate oxygen-38 involved in a combination of partial oxidation - reforming - body of water gas shift reaction to produce a synthesis gas product stream 40.

比较理想的是,除了反应物入口附近外,通过调节反应物进料组成(例如,增加水蒸汽含量有利于吸热蒸汽重整反应)、氧气渗透作用(例如,改变含氧气流10的压力或流速)、复合膜的形态、和/或催化剂活性(例如,改变重整催化剂的表面积或Ni填充量),来控制混合反应接近能量中立,从而控制氧气传输膜管的膜温。 Ideally, the reaction near the inlet in addition, by adjusting the composition of the reactant feed (e.g., increasing the water vapor content favor the endothermic steam reforming reaction), oxygen permeation (e.g., changing the pressure of the oxygen-containing gas stream 10 or flow rate), the form of the composite film, and / or catalytic activity (e.g., change the surface area or the reforming catalyst filling amount of Ni), close to the reaction mixture to control the energy neutral, in order to control film temperature of oxygen transport membrane tubes.

合成气产品气流40在第二热交换器39中逆着反应气流38被冷却。 Synthesis gas stream 40 against the reaction product gas stream 38 is cooled in the second heat exchanger 39. 为避免金属粉尘化,任选地保持第二热交换器39的壁温在约400℃以下比较理想,因此在所述交换器中,反应物进料一侧比合成气产品一侧具有更高的热传递膜系数,不需要使用昂贵的材料。 In order to avoid metal dusting, optionally holding the second heat exchanger 39 is ideal wall temperature below about 400 ℃, thus the exchanger, the reactant feed side than the side of the syngas product having a higher heat transfer film coefficient, without the use of expensive materials. 这可由反应物进料一侧比产品气体一侧具有更高的质量流速或薄层流中更小的渠道尺寸来实现。 This reactant feed side may have a smaller channel size or layer higher mass flow rate than the product gas stream side to achieve. 这样可以限制反应气流38在进入反应区域之前可以被加热达到的温度。 This limits the reaction gas stream 38 before entering the reaction zone may be heated to reach a temperature. 为避免入口点附近的氧气传输膜管冷却至过低的温度,从而影响离子的有效传输,在膜相反一侧的含氧气流10的局部温度应该比反应气流38的温度高出许多。 To avoid oxygen transmission membrane tubes near the entry point was cooled to too low a temperature, thus affecting the efficient transfer of ions, the gas flow should the local temperature at the opposite side of the membrane oxygen-containing gas stream 10 than the reaction temperature of 38 higher. 可任选地省略反应气流38入口点附近的反应区域26内的催化剂,这样做同样是有利的,可以有利于反应区域26入口部分的氧化反应和反应物的快速加热。 May optionally be omitted in the catalyst reaction zone 26 near the entry point of the gas flow 38, also advantageous to do so, it may facilitate rapid heating and oxidation of the reactants inlet portion 26 of the reaction zone.

避免金属粉尘化的一个任选的替换方法是,在合成气产品气流40从反应区域26中排出点附近注入淬灭水气流44,以冷却合成气产品气流40。 An optional alternative method is to avoid metal dusting, the syngas product stream 40 is discharged from the reaction zone near the point of injection quenched with 26 water stream 44 to cool the syngas product stream 40. 避免金属粉尘化的另一个任选的替换方法是,在第二热交换器39中将合成气产品气流40只冷却到700℃温度以上,然后转移到锅炉46进行进一步冷却,因为沸水在低温一侧,很容易保持壁温在400℃以下。 Another optional alternative method to avoid metal dusting, in the second heat exchanger 40 in the syngas product stream 39 is cooled to a temperature above 700 deg.] C, and then transferred to the boiler 46 is further cooled, as a low boiling water side, it is easy to maintain the wall temperature below 400 ℃.

通常,在离开第二热交换器39以后的合成气产品气流40中存在足够显著的热量,在理想的工艺压力水平下,可用来增加锅炉46中反应气流38的需求量。 Typically, there is sufficient heat in significant after leaving syngas product stream 39, a second heat exchanger 40, in an ideal process pressure level, can be used to increase the demand for reactive gas stream 46 in boiler 38. 从锅炉46出来后的合成气产品气流40进入废热锅炉48,在废热锅炉48内,合成气产品气流40进一步被冷却,所含的大部分水蒸汽被低压下的沸水凝结。 Syngas product gas stream 46 from the boiler 40 into the waste heat boiler 48, in the waste heat boiler 48, the synthesis gas product stream 40 is further cooled, most of the water vapor contained in the boiling water is condensed at low pressure. 从废热锅炉48出来的合成气产品气流40进入一个水分离器50,在后处理区域52内进一步处理,得到处理过的产品气流54。 From the waste heat boiler 48 out of the syngas product stream 40 enters a water separator 50, after further processing in the processing region 52, a treated product stream 54. 后处理包括用已知的方法除去酸气和调整氢气和一氧化碳的比例。 After treatment includes acid gas removal and adjustment of the ratio of hydrogen and carbon monoxide by known methods.

处理后的产品气流54的一部分56通过循环压缩机58以循环气流32再次循环进入天然气气流30中。 Product gas stream 54 is treated by a portion of 56 to recycle compressor 58 into the recycle stream 32 is recirculated natural gas stream 30. 循环气流32也可以与来自下游反应器的循环气流汇合。 Recycle gas stream 32 may be merged with the recycle stream from a downstream reactor. 任选地,将从后处理区域52分离得到的二氧化碳加入到循环气流32(未标出)中,以调节反应气流38中碳和水蒸汽的比例以及合成气产品中氢气和一氧化碳的比例。 Optionally, the carbon dioxide from the post-treatment area 52 is added to the separated recycle gas stream 32 (not shown) in order to adjust the proportion of water vapor and carbon 38 and the ratio of the reaction product stream of synthesis gas of hydrogen and carbon monoxide. 最终合成气产品气流60被传递到下游工序,例如生产甲醇的工序或费托法生产液体燃料的工序。 The final synthesis gas product stream 60 is passed to a downstream process, such as the production of liquid fuel production process of the Fischer-Tropsch process or methanol.

从水分离器50和补充水气流64中得到冷凝水流62,用泵66使它达到理想的压力,并在锅炉46中把它转变为蒸汽,这就形成了蒸汽气流36。 From the water separator 50 and the supplemental gas stream 64 is condensed to obtain water flow 62 by a pump 66 to bring it to the desired pressure and the boiler 46 into steam in it, which are formed steam stream 36. 蒸汽气流36汇合天然气气流30形成反应气流38。 Steam stream 36 and gas stream 30 confluence reactive gas stream 38 are formed. 废热锅炉48中产生的蒸汽可以用来为固定压缩机的蒸汽涡轮机引擎提供动力或用于其他现场用途。 Steam generated in the waste heat boiler 48 may be used to provide power for other on-site use or as a fixed compressor, steam turbine engines.

任选地,第二热交换器39分为两部分,并且两部分之间有一个催化预重整器。 Optionally, the second heat exchanger 39 is divided into two parts, and has a pre-reformer catalyst between the two parts. 催化预重整器的操作温度在约400℃到约500℃之间,其提高了反应气流38在入反应区域26之前,可以进行加热达到并且没有生成单体碳的允许温度。 Operating the pre-reformer catalyst at a temperature between about 400 deg.] C to about 500 ℃, which increases the monomers and does not generate carbon gas stream 38 before allowing the temperature of the reaction 26 may be heated to the reaction zone reached. 如果在预重整器中被转化的反应物进料包含比甲烷重的碳氢化合物,则这种任选情况特别有用。 If the pre-reforming reactor to be converted reactant feed comprising hydrocarbons heavier than methane, which is particularly useful in the case optionally. 在这种情况下,任选添入空气气流24和任选加入燃料气流22是特别有用的,因为燃料与包含的氧气的反应把热能增加给含氧气流10,为预重整器中的吸热反应至少提供一些需要的热量。 In this case, the air stream 24 and the optional insertion of fuel gas stream 22 is optionally added particularly useful, because the fuel with oxygen contained in the reaction of oxygen containing gas stream 10 to increase the heat, in the pre-reformer is an endothermic reaction providing at least some of the heat needed.

参考图2,含氧气流10经入口通道68送入反应器72的下头70中。 Referring to FIG 2, the oxygen-containing gas flow passage 10 through the inlet 68 into the lower head 70 of the reactor 72. 在进入反应器72之前,含氧气流10如上面讨论的那样被增压和加热。 Before entering the reactor 72, as is pressurized and heated oxygen-containing gas stream 10 as discussed above. 在下头70和第一热交换器20内,被增压的原料空气被经排放通道74离开反应器72的热贫氧气流18(也称滞留物或阴极流出物),加热到约700℃至约1000℃的温度范围内。 In the first heat exchanger 20 and the nod 70, the pressurized feed air is discharged through the passage 74 leaving the reactor 72 heat the oxygen-depleted stream 18 (also called retentate or cathode effluent), heated to about 700 deg.] C to within the temperature range of about 1000 ℃.

来自含氧气流10中的热压缩原料空气,向上流经热交换器管76进入末端开口的喷管78中。 Hot oxygen-containing gas stream from compressed feed air 10, flows through heat exchanger tubes 76 upwardly into the end of the nozzle 78 opening. 每支喷管的顶部由一端封闭,另一端开口型的氧气传输膜管80覆盖。 Each nozzle is closed by the top end and the other end open type oxygen transport membrane tube 80 covers. 在每支喷管78的开口端,热压缩空气逆着氧气传输膜管80内表面排放,然后向下流去。 Each nozzle 78 at the open end, the hot compressed air against the surface of the oxygen transport membrane tube discharge 80, and then flows down to. 当热压缩空气在喷管78和氧气传输膜管80之间的环形内向下流动,空气中的氧气被离子化,以离子形态径向穿过膜渗入阳极一侧29,在这里,它与反应气流的反应气体反应。 When the flow of hot compressed air within the annulus 80 between the nozzle 78 and the oxygen transport membrane tubes, oxygen in the air is ionized to form ions penetrate radially through the anode side of the membrane 29, where it is the reaction the reaction of the reaction gas stream. 反应产品和可能的少量残余氧气将流入催化剂床28。 The reaction products and possible traces of residual oxygen flowing into the catalyst bed 28. 在环形的下端,贫氧空气作为贫氧气流18从排放通道74流出之前,流经第一热交换器20和下头70。 In the lower end of annular, oxygen-depleted air as the oxygen-depleted gas stream 18 from the effluent prior to discharge passage 74, flowing through the first heat exchanger 20 and the lower head 70.

从图2中可以看出,在反应器72的上部,反应气流38经上入口通道82进入上头84,接着进入第二热交换器39,在这里,通过经排放通道86离开反应器72的合成气产品气流40(也称阳极流出物),反应气流38被加热到高达约750℃的温度范围。 As can be seen from Figure 2, the upper portion of the reactor 72, the reaction gas flow passage 38 through the inlet 82 into the top 84, and then enters the second heat exchanger 39, where the synthesis reactor 72 via the discharge passage 86 exit through product gas stream 40 (also referred to as anode effluent), reactive gas stream 38 is heated up to about 750 deg.] C temperature range. 反应气流38在约100psig至约600psig的压力下进入装置1。 The reaction gas stream 38 enters apparatus 1 at a pressure of from about 100psig to about 600psig.

反应气流38离开第二热交换器39后,流入催化剂床28,以轴向流、反交叉流、或螺旋交叉流的形式横向通过催化剂床28。 The reaction stream 38 exiting the second heat exchanger 39 after flowing into the catalyst bed 28, axial flow, cross-flow anti, or a spiral form cross-flow laterally through the catalyst bed 28. 它与氧气传输膜管80产生的并进入催化剂床28的渗透氧接触。 It generates oxygen transmission membrane tube 80 and into the catalyst bed 28 in contact with the permeate oxygen. 优选的碳氢化合物气体是包含甲烷和其他轻质碳氢化合物的天然气。 The preferred hydrocarbon gas comprising methane and other light hydrocarbon gas.

放热部分氧化反应和吸热重整反应都发生在催化剂床28内的氧气传输膜管的阳极29一侧。 Exothermic partial oxidation reaction and the endothermic reforming reaction occurs in the anode catalyst bed oxygen transmission film in a tube 2829 side. 甲烷的部分氧化反应见方程1。 Partial oxidation reaction of methane see equation 1. 甲烷的蒸汽重整应见方程2。 Steam reforming of methane should see equation 2. 一氧化碳的其它转化通过放热水煤气转换反应,见方程3发生。 Other conversion of carbon monoxide by the exothermic water gas shift reaction, see Equation 3 occurs.

(1)(2)(3)本发明的范围还包括甲烷和二氧化碳之间的重整反应,如方程4所示。 (1) (2) (3) the scope of the present invention further includes reforming reactions between methane and carbon dioxide, as shown in Equation 4. 在工艺进料的不同蒸汽-碳比例下操作,可调节合成气产品H2/CO的比例。 In various feed process steam - operating on carbon ratio, the ratio may be adjusted syngas product H2 / CO of. 类似地,通过改变蒸汽-碳的比例,可以调节放热和吸热反应之间的整体热平衡。 Similarly, by changing the steam - carbon ratio can be adjusted the overall heat balance between exothermic and endothermic reactions.

(4)当反应气流38流经包含反应区域的催化剂床28时,它与渗透氧反应。 (4) when the gas stream 38 flows through the catalyst bed reactor comprising a reaction zone 28, it reacts with the permeate oxygen. 在氧化反应中,在氧气传输膜管80的密实膜的阳极一侧29的渗透氧与反应气流38供给的反应气体反应。 In the oxidation reaction, the oxygen supply 29 and the permeate gas stream 38 of the reaction the reaction gas in the reaction tube anode side of oxygen transport membrane film 80 is dense. 氧化反应产品流经任选的多孔罩管88并进入催化剂床28,其中多孔罩管88环绕在每支氧气传输膜管80的周围。 The oxidation reaction product flowing through optional porous shield tubes 88 and 28 into the catalyst bed, wherein the porous shield Each tube 88 surrounds the oxygen transport membrane tube 80. 当它流经催化剂床28时,这些气体与反应气流38反应生成合成气(CO+H2)。 When it flows through the catalyst bed 28, the reaction of these gases with the reaction stream 38 to syngas (CO + H2).

催化剂床28内的工艺气体流动通道可以采用不同的构型。 The catalyst bed in the process gas flow passage 28 may take different configurations. 图2描述了工艺气体以轴向流动方式向下和横向穿过催化剂床。 2 depicts a flow of the process gas in an axial manner and transversely downwardly through the catalyst bed. 这可由所示的横向分段挡板89的排列来实现。 This may be transversely segmented baffle arrangement 89 shown implemented. 合成气被收集在催化剂床28下面的下部气室90中,然后通过合成气传递管或导管92向上传输到催化剂床28上面的上部气室94。 Synthesis gas is collected below the catalyst bed 28 in the lower plenum 90, and then synthesis gas delivery tube or conduit 92 into the catalyst bed 28 upwardly transmitted in upper chamber 94 above. 然后如上所述,合成气进入第二热交换器进行热量回收。 Then as described above, the synthesis gas into a second heat exchanger for heat recovery.

删除挡板89可以得到另一种流动排列方式,这样通过催化剂床29的流动主要在轴向方向。 Remove the baffle 89 can be obtained another flow arrangement, so that the main flow of catalyst bed 29 in the axial direction. 另一种选择是轴向-螺旋混合流。 Another option is axially - helical mixing flow. 工艺气体在段间轴向流动,在每个连续段面由挡板100导向为向内或向外的螺旋流。 The process gas flows axially between the segments in each successive segment of the guide surface 100 by the shutter inward or outward spiral flow. 这种方式描述在图3中。 This embodiment is described in FIG. 另一个可选择的流动是径向分段交叉流构型,其中过程气体将横向流过OTM管,该OTM管处于由径向壁102和与径向壁102连接的垂直末端板103限定的分段催化剂室101内。 Another alternative is to flow radially segmented cross-flow configuration, where the process gas flows across the OTM tubes, the tube is in OTM radial wall defined by the vertical end plate and a radial wall 102 connecting points 102 103 section 101 within the catalyst chamber. 每个室可以包含一个或多个氧气传输膜管80。 Each chamber may contain one or more oxygen transport membrane tubes 80. 工艺气流收集在中间气室内,它径向延长到在末端壁103和包含在每个分段催化剂室101内的催化剂之间的催化剂床的全长。 Process gas stream collected in the middle of the air chamber, which extend radially to the entire length of the catalyst bed between the end wall 103 and the catalyst contained within the catalyst chamber 101 of each segment of. 每个气室带有为气体在连续催化剂室之间进行混合的装置。 Each air chamber is mixed with the apparatus between successive catalyst chamber is a gas. 图4展示了这一构型。 FIG. 4 shows this configuration. 连续的催化剂室的数目可以是大于或等于1的任何数字。 The number of successive catalyst chamber may be any number greater than or equal to 1. 这些室可以是如图4所示的那样,以某种径向方式空间定位,或者是其它的横向构造,例如如图5中所示的,挡板104横向、错列、垂直排列。 These chambers may be as shown in FIG 4, in some way a radial space is positioned, transverse, or other configurations, as shown in FIG. 5, the lateral baffle 104, staggered, vertically aligned.

催化剂床28由蒸汽重整催化剂的填充颗粒组成,该催化剂通常已知在蒸汽甲烷重整(SMR)氢气生产装置中使用。 The catalyst bed of filler particles 28 by the steam reforming catalyst composition, the catalyst is generally known to use a steam methane reforming (SMR) hydrogen production facility. 通常,催化剂包含沉积在相容衬底载体材料例如矾土的活性镍层。 Typically, the catalyst comprises a support material deposited on the substrate compatible active layer, such as nickel-alumina. 颗粒可以为多种几何形状,但通常选择能为工艺气体提供足够接触面积的颗粒,而将气体流动造成的压力降低减小到最小。 The particles may be various geometries, but is generally selected to provide a sufficient contact area of ​​the particles is a process gas, and the pressure reduction caused by the gas flow reduced to a minimum. 径向分段交叉流方式在连续催化剂室之间为改变催化剂活性提供了一种有用的方法,从而以热中和方式,没有经历个别热点或淬灭区,促使工艺气体理想地转变为合成气。 Radial cross-flow sections between the successive catalyst chamber provides a useful way to vary the catalyst activity so as to avid manner and without experiencing quenching zone or individual hot spots, cause the process gas converted to synthesis gas over the .

为了在采用向上床流的轴向流反应器中获得改变工艺气体转变的理想效果的另一种方式是,使用如图6所示的不同长度的氧气传输膜管80。 In order to use an axial flow bed flow reactor in another manner to achieve the desired effect of changing the process gas is converted using an oxygen transport membrane tubes 80 of different lengths as shown in FIG. 6. 这提供了在催化剂床28内改变每单位体积氧气释放的一种方式,因此在较高管密度区域,强调部分氧化反应胜过重整反应。 This provides a way to change the release of oxygen per unit volume in the catalyst bed 28, thus higher tube density region, partial oxidation reaction stressed than reforming reactions.

再参考图2,在启动过程中,使用一种商业上可得的喷嘴混合燃烧炉105来为反应器提供热量。 Referring again to FIG. 2, during startup, the use of a commercially available nozzle mixing burner 105 to provide heat for the reactor. 空气和天然气供应到燃烧炉105,它的火进入支持氧气传输膜80的管板106的正下方的低压空气室。 Air and gas supplied to the burner 105 which fires into the oxygen transport membrane tube support plate 80 immediately below the low pressure air chamber 106. 反应器72和包含氧气传输膜管在内的内部组件的加热速度由燃烧炉的燃烧速率和进料空气流速控制。 The heating rate and the internal components of reactor 72 comprising oxygen transmission membrane tubes from the inner burner firing rate and the feed air flow rate control. 当操作温度达到稳定状态并且真正开始生成合成气时,整个反应将变为放热反应,不再需要从燃烧炉104输入热能。 When the operating temperature reaches a steady state and actually starts to generate synthesis gas, the overall reaction becomes exothermic reaction, the thermal energy input is no longer required from the furnace 104.

这个反应器设计提供了四个内部零件组合,它们可以彼此相互独立地自由膨胀或收缩,不会引起机械负荷以及造成材料应力。 The reactor design provides a combination of four internal parts, independently of each other they may be freely expanded or contracted, and does not cause mechanical loads caused material stresses.

参考图7,装置1的一个内部零件组合是一组一端关闭的OTM管80,在其开口端被固定管板106密封。 Referring to Figure 7, the internal parts of a combination apparatus 1 is a set of closed end tube 80 OTM, seal 106 is fixed to the tube plate at its open end. 氧气传输膜管80将不受热膨胀和组分扩张的限制,垂直向上伸长。 Oxygen transport membrane tubes 80 will not limit the expansion of components and thermal expansion, vertically elongated upward. 管板106通过法兰盘107与反应器72的外壳73相连。 Plate 73 is connected by a pipe flange 106 of the housing 107 of the reactor 72. 氧气传输膜管80通过下文中将讨论到的管密封件126与管板106相连。 Oxygen transport membrane tubes 80 are connected to the tube seal 126 and tube sheet 106 discussed later.

能够传导离子和电子的任何陶瓷膜材料或材料的组合都可以用来制造氧气传输膜管80。 Compositions capable of conducting ions and electrons ceramic membrane material or any material can be used to produce oxygen transport membrane tubes 80. 具有混合传导性(离子和电子传导性)的金属氧化物和传导离子的金属氧化物和传导电子的金属氧化物或金属的两相混合物都可以应用。 Metal oxide and a metal oxide ion-conducting two-phase mixture having a mixed conducting (ion and electron conductivity) and the electron-conducting metal or metal oxide can be applied. 在上面引用到的参考文献中公开的混合传导钙钛矿、黄褐针镍矿和两相金属-金属氧化物是特别适合的。 Mixing disclosed in the above-cited references conductive perovskites, yellowish needles and a two-phase nickel metal - metal oxide is particularly suitable. 氧化传输膜管80有密实的壁或是复合形式,其中密实膜由优先在反应区中或阳极一侧29的多孔基质支撑。 Oxide film transfer tube 80 has the form of a composite or dense wall, in which a dense film is formed preferentially in the reaction zone or the anode side of the porous substrate support 29. 在这种情况下,至少多孔载体的外层可以包含催化剂。 In this case, at least the outer layer may comprise a porous catalyst support. 因此在膜阳极一侧29,至少一部分吸热重整反应具有与氧化反应更近的热传递关系。 Thus the anode side of the membrane 29, at least a portion of the endothermic reforming reaction and the oxidation reaction has a closer heat transfer relationship. 优选使用薄、牢固的膜,其具有用于高氧气回流的高氧气空白浓度,且具有足够的管强度保持可以接受的可靠性。 Preferably a thin, solid film having a high oxygen concentration blank for a high oxygen reflux tube and having sufficient strength to maintain an acceptable reliability. 本发明还可以使用其他膜结构(例如,陶瓷膜材料的平板)来代替管。 The present invention may also use other membrane structures (e.g., a ceramic plate film material) in place of the tube. 在一些应用中,也可以在阴极和阳极两侧上用多孔离子和电子传导涂料或类似物涂布膜材料,以增加表面交换面积以及提高它的传质性能。 In some applications, the coating may be a conductive coating film or the like with a porous material ions and electrons on the cathode and anode sides, to increase the surface area of ​​exchange and mass transfer to enhance its performance.

陶瓷膜可包括任何选择性传导氧离子的材料。 Ceramic membrane may comprise any material selectively conducts oxygen ions. 下表列出了这类材料的几个例子。 The following table lists several examples of such materials.

表1: 混合传导固体电解质 Table 1: mixing conductive solid electrolyte

参考图8,氧气传输膜管80将在反应区域26内自由滑动,其中反应区域26由催化剂床28限定,并且催化剂床28中分散有任选多孔罩管88。 Referring to Figure 8, the oxygen transport membrane tubes 80 will slide freely within the reaction zone 26, wherein the reaction zone 26 is defined by a catalyst bed 28, catalyst bed 28 and dispersion tubes 88 with an optional porous shield. 罩管88围绕在每个氧气传输膜管80的周围,在通过陶瓷膜壁传输的氧气和催化剂床28之间形成一种气体连通装置。 The cover tube 88 surrounds each oxygen transport membrane tube 80, to form a gas through the ceramic membrane 28 between the wall and the catalyst bed oxygen transmission communication apparatus. 任选的罩管88也为去除和重新插入氧气传输膜管,或没有催化剂床-管的相互作用下去除和替换催化剂,提供了一个方法。 Optionally a cover tube 88 is also removed and reinserted into the oxygen transport membrane tubes, or without a catalyst bed - the interaction of catalyst removal and replacement of the tube, there is provided a method. 催化剂床28被支撑物110支撑在下面的固定的氧气传输膜管板106上,并且能够根据需要没有限制的因热膨胀而垂直向上伸长。 The catalyst bed is supported on a support 28 fixed below the oxygen transport membrane tube sheet 106 110, and can be elongated vertically upward due to thermal expansion without limitation according to need.

另一个内部零件组合由第二热交换器组成。 Another combination of the internal parts of the second heat exchanger components. 第二热交换器39整个包括在反应器72内,其中反应器72内部用陶瓷纤维绝热毯112绝热。 The second heat exchanger 39 is included in the entire reactor 72, wherein the inside of the reactor 72 with a heat insulating ceramic fiber insulating blanket 112. 第二热交换器39受固定管板114的支撑,它把进来的原料气流与出去的产品气流隔离开。 A second heat exchanger tube 39 is fixed by the support plate 114, to which the incoming feed gas stream with the product stream out of the isolate. 因为热交换器内的温度曲线是建立在顶部的冷端和底部的热端之间,热交换器39自由地朝着氧气传输膜管80轴向膨胀。 Because the temperature profile within the heat exchanger is established between the hot end and cold end of the bottom of the top, the heat exchanger 39 toward the free oxygen transport membrane tubes 80 axial expansion. 如图2所示,反应气流38被引导在第二热交换器39的热交换管115产品一侧的壳上流动,并收集在催化剂28上的敞开空间内。 As shown, the reaction gas stream 238 is directed to flow on the shell side of the heat exchanger product tube 115 of second heat exchanger 39 and collected in the catalyst 28 in the open space. 形成合成气产品气流40的合成气产品流经热交换管的内部。 Forming the syngas product stream flowing through the interior of the syngas product 40 of the heat exchange tubes.

参考图9,在热膨胀时能自由伸长的其它内部零件组合是第一热交换器20。 Referring to Figure 9, other internal parts of the combination can be freely upon thermal expansion of the first heat exchanger 20 is elongated. 通过在两个反应器法兰盘118之间固定其管板116,将第一热交换器20安装在反应器内,第一热交换器20作为从氧气传输膜管80内部出来的热贫氧气流18中回收热能的装置。 By fixing tube sheet 116 between which two flanges the reactor 118, the first heat exchanger 20 is mounted within the reactor, as a first heat exchanger 20 out from the inside of the oxygen transport membrane tubes 80 heat the oxygen-depleted It means the stream 18 recovered thermal energy. 第一热交换器20被挡板120隔成几段,相对于管侧流动,挡板120引导壳侧流动以反交叉流动的方式进行。 A first heat exchanger 20 is separated into paragraphs shutter 120, relative to the tube side flow baffle 120 for guiding the shell side flow in a manner counter-crossflow. 当贫氧气流18流经第一热交换器20时,它把热能传递给进来的含氧气流10。 When the oxygen-depleted gas stream 18 flowing through the first heat exchanger 20, it passes the heat to the incoming gas stream 10 containing oxygen. 如图1所示,含氧气流10通过小直径开端喷管78传递到氧气传输膜管80的内部,其中小直径开端喷管78向内延伸到盖端附近的位置。 1, the oxygen-containing gas stream 10 through a small diameter nozzle 78 is transmitted to start the internal oxygen transport membrane tube 80, where the beginning of the small diameter nozzle 78 extends inwardly to a position near the end of the cap. 在这些开端喷管78和氧气传输膜管80的盖子的内表面之间的轴向距离将提供第一热交换器20垂直上升热增长的空间。 The axial distance between the beginning of the nozzle cap 78 and the oxygen transport membrane tube 80 will provide the inner surface of the space 20 in vertical upward heat exchanger of the first growth.

热交换器设计更充分展示在图10的横截面视图中。 Heat exchanger designs appear more fully cross-sectional view of FIG. 10. 例如,第一热交换器20被陶纤维毯绝热体112和反应器72的反应器壁73所包围。 For example, a first heat exchanger 20 is ceramic fiber blanket insulation 73 surrounding the reactor 112 and reactor wall 72. 螺旋挡板122引导气体以反交叉流或螺旋取向流在通道124内流动。 Spiral baffle 122 to direct the gas cross-flow or counter-current flow in a helical orientation within the channel 124. 对后者来说,垂直定位的热交换器管76展示在流动通道124内,穿透螺旋挡板122引导轴向流动。 For the latter, the vertical heat exchanger tubes 76 positioned within the flow channel display 124, the shutter 122 penetrates the coil axially guiding the flow. 通过限制壳侧流体气流进入限定的渠道,控制截面流面积可获得更高的对流系数。 By limiting the gas flow into the shell-side fluid channels defined, cross-sectional flow area control can achieve higher convection coefficient. 而且,螺旋型挡板122能延伸表面到热交换器76的管壁,进行辐射热传递。 Further, the helical baffle 122 can extend to the wall surface of the heat exchanger 76, radiation heat transfer. 相对于传统的带有交叉流挡板的壳-管热交换器,螺旋流动设计能获得更大的整体热传递系数。 With respect to the conventional cross-flow baffle shell - tube heat exchangers, spiral flow designed to achieve greater overall heat transfer coefficient.

氧气传输膜管-管板密封物126要求密封高压燃料气流和低压含氧气流之间的区域,这个地方是管与高压管板结合处。 Oxygen transport membrane tubes - tube sheet seal 126 seals the region between the required high pressure fuel gas stream and a low pressure oxygen-containing gas stream, this place is the high-pressure pipe junction tube sheet. 任何高温燃料渗入氧化物气流都有害于反应器的安全操作。 Any penetration of the oxide high-temperature fuel gas stream are detrimental to safe operation of the reactor. 局部的燃烧喷射能够形成,其可毁坏密封物126,氧气传输膜管80或管板116。 Local fuel injection can be formed, which can destroy the seal 126, the oxygen transport membrane tubes 80 or tube sheet 116.

附图11介绍了一种装置,通过中间缓冲气体隔开燃料和空气气流,来限制这种不利的接触。 Figure 11 describes a device, fuel and air are separated by an intermediate buffer gas stream, to limit this negative contact. 缓冲气体不应该支持燃料的氧化反应。 The buffer gas should not support the oxidation reaction of the fuel. 依据密封材料的选择,气体例如氮气、二氧化碳或蒸汽是可以接受的对象。 Selected based on the sealing material, such as nitrogen gas, carbon dioxide or steam is acceptable objects. 适合的密封设计的详细说明在US 6,139,810中给出,参见附图3和4。 Suitable seal design details are given in US 6,139,810, referring to Figures 3 and 4. 密封是用一缓冲气体在管板106处的密封物126和金属板127处的密封物128之间分两个阶段实现,它把缓冲区域130从反应产品中隔离开来。 The seal 128 between the two stages is implemented in a sealing seal 126 and the metal plate 127 of the tubesheet 106 with a buffer gas, the buffer area 130 which is isolated from the reaction product. 与密封物126相邻的缓冲区域或室130被通过通道132的缓冲气体充满,并且维持在稍高于燃料气流的压力。 130 and 126 or the buffer area adjacent to the chamber through a channel seal 132 is filled with buffer gas, and maintained at a pressure slightly higher than the fuel stream. 减少压力差别到最小,和/或利用第二套机械密封物代替氧化传输膜管80周围的密封物128,可以控制这种缓冲气体渗入高压燃料气流。 Reduced to a minimum pressure difference, and / or with mechanical seals 80 around the second set of transmission replacing oxide film tube seal 128, such a buffer gas may be controlled penetration of the high pressure fuel stream. 如果用蒸汽和或CO2作为缓冲气体,少量的泄漏无关紧要,并能够容许。 If steam or CO2 as a buffer gas and a small amount of leakage does not matter, and can be tolerated. 因为这些气体也是反应气流的组分。 Because these gases are reactive components of the gas stream. 在这种情况下,在OTM管和金属板127的开端之间,使用一个紧密环状间隙作为流量限制,或非接触曲折的密封物就足够限制渗漏到允许的水平。 In this case, the OTM tubes between the beginning and the metal plate 127, to use a tight annular gap as a flow restriction, a non-contact seal tortuous enough to limit leakage to an acceptable level. 缓冲气体向空气气流中的泄露将依赖于在氧气传输膜管80和管板106之间的密封物126的质量。 Buffer gas leakage into the air stream will depend on the quality of the seal between the oxygen transport membrane tube 80 and the tube 126 of the plate 106.

实现本发明其它方法包括:内部工艺气体和空气流动方式的变化,这已经在前面描述过;构造不同形式的催化剂;热交换器设计的变化,但是排除两个热回收热交换器中的任何一个;以及包括环绕在部分反应外部器壁73周围的环形夹套,进行额外的热回收和进料空气预热。 Other methods of implementing the present invention comprises: an internal process gas flow pattern change and air, which had been described previously; various forms of catalyst configurations; heat exchanger designs change, but the exclusion of any one of two heat recovery heat exchanger ; and a jacket surrounding the annular wall 73 surrounding the outer portion of the reaction, additional heat recovery and preheating the feed air.

催化剂也能放置在刚性的开放蜂巢式独石中,它被成型来利用严密填充的氧气传输膜管80的几何形状。 The catalyst can also be placed on a rigid monolithic open cellular, which is molded using a geometry closely packed oxygen transport membrane tube 80. 网状泡膜或提供高的表面积的催化剂载体的其它方式都可以用。 Reticulated foam film or otherwise provide a catalyst support of high surface area can be used. 可能的形状包括单个空圆柱状套筒,它能在氧气传输膜的外表面滑动,连锁蜂巢片段,它能在氧气传输膜管上滑动,并且相互配合以维持一个类似填充的催化剂床的结构,或者单个突出杆,它能轴向插在相邻氧气传输膜管之间。 Possible shapes include a single cylindrical sleeve blank, which can slide on the outer surface of the oxygen transport membrane, honeycomb chain fragments, which can slide on the oxygen transport membrane tubes, the structure and cooperate to maintain a similar catalyst packed bed, or a single projecting rod, which can axially interposed between adjacent membrane tubes oxygen transmission.

内部热交换器设计也可以有其它方式,包括常见的分段的或“圆盘和饼圈”折流的壳-面流动方式。 Internal heat exchanger designs may also have other ways, including the common segmented or "disc and donut" shell baffled - surface flow pattern. 使用这些技术可以减少早先描述过的优选轴向-螺旋构型的壳-面热传递系数。 Using these techniques preferably axially described earlier may be reduced - helical conformation of the shell - surface heat transfer coefficient.

再次参考图2,当反应气流38包含非甲烷的高级烃时,为避免由于形成碳或结焦引起的操作问题,包含一个预重整工艺步骤是有利的。 Referring again to Figure 2, when a non-reactive gas stream 38 containing methane to higher hydrocarbons, to avoid operational problems due to the formation of carbon or coke caused by a pre-reforming process comprising the steps is advantageous. 为此由一个催化剂床134组成的预重整器和装置1合并,其方式是第一热交换器20被分成两个分开部分136和138,催化剂床134的每一面各有一部分。 For this purpose the pre-reformer and means consists of a catalyst bed consisting of a combined 134 in a manner that the first heat exchanger 20 is divided into two separate portions 136 and 138, 134 on each side of each portion of the catalyst bed. 第一部分136预热含氧气体气流10,升高它的温度到预重整器通常具有的水平,约450℃到约550℃。 The first portion 136 preheated oxygen-containing gas stream 10, raising its temperature to a pre-reformer typically have a level of about 450 deg.] C to about 550 ℃. 第二部分138提供最终热交换,把预重整气体提升到约700℃到约1000℃的温度范围内。 The second portion 138 to provide the final heat exchanger, the pre-reformed gas is raised to a temperature range of from about 700 to about 1000 ℃ deg.] C of.

图12描绘了一个可任选的从装置1中回收额外热量的环状外套,否则该额外热量将是环境热能泄漏的一部分。 12 depicts a device 1 optionally recovering additional heat from the outer ring, additional heat which would otherwise be part of the environment the heat leak. 部分反应器壁73可用一薄金属套142包裹,形成一环状流动通道144,用来预热含氧气流10。 Parts of the reactor wall 73 can be used a thin metal sleeve 142 wrapped, forming an annular flow channel 144, to preheat the oxygen-containing gas stream 10. 被预热的含氧气流10经过通道146被导入第一热交换器20进一步加热。 The preheated oxygen-containing gas 146 is introduced into passage 10 through a first heat exchanger 20 is further heated. 该外套法要求压力容器的这部分的内部绝热体的厚度“t”应该稍微减少,以升高壁温,提高温差,改善热传递。 The thickness of the jacket inside the pressure vessel law requires insulation of this part of the "t" should be slightly reduced to raise the wall temperature, the temperature difference increase, improved heat transfer. 反应器壁73上升的温度,不能把相应材料的强度降低到安全容纳内部反应器压力的要求以下。 The reactor temperature rising wall 73, can not reduce the strength of the material corresponding to the safety requirements of the internal reactor pressure receiving less.

参考具体实施方案,尽管本发明已经在上面进行了描述,但是在不脱离本发明创造性的理念的前体下,本发明可以进行许多变化、修改和改变。 With reference to specific embodiments, although the present invention has been described above, without departing from the inventive concept of the precursor of the present invention, the present invention many variations, modifications and changes. 因此本发明包含这些所有的变化、修改和改变,它们都落入本发明所附的权利要求的精神和范围内。 Therefore, the present invention covers all variations, modifications and variations which fall within the spirit and scope of the appended claims.

Claims (10)

1.一种生产合成气的装置,包括:反应器(72);第一热交换器(20),位于所述反应器一端内,通过与贫氧气流(18)间接热交换来加热预热的含氧气流(10);第二热交换器(39),位于所述反应器(72)另一端内,通过与合成气产品气流(40)间接热交换来加热包含至少一种碳氢化合物和蒸汽的反应气流(38);若干氧气传输膜(80),位于反应器(72)的反应区域(26)内,把氧气从含氧气流(10)中分离出来,由此在氧气传输膜(80)的阳极一侧得到渗透氧,氧气传输膜(80)阴极一侧与第一热交换器(20)联通,以接收含氧气流(10);反应区域(26)与第二热交换器(39)联通,以便使反应气流(38)进入所述反应区域内的氧气传输膜(80)的阳极一侧;催化剂床(28)位于反应区域(36)内,在组合的部分氧化-重整-水煤气转换反应中,促进渗透氧的反应,从而产生合成气产品气流(40);第一进入和排放通道(68,7 1. An apparatus for producing synthesis gas, comprising: a reactor (72); a first heat exchanger (20), positioned within said end of the reactor, preheated by the heated oxygen-depleted gas stream (18) indirect heat exchange the oxygen-containing gas stream (10); a second heat exchanger (39), located in said reactor (72) the other end to at least one hydrocarbon comprising heating the syngas product stream by (40) an indirect heat exchange Some oxygen transmission membrane (80), a reaction zone (26) of the reactor (72), the oxygen separation from oxygen-containing gas stream (10) out, whereby the oxygen transmission membrane; and a reactive gas stream of steam (38) (80) obtained in the anode side permeate oxygen, the oxygen transport membrane (80) on the cathode side of the first heat exchanger (20) Unicom to receive oxygen-containing gas stream (10); a reaction zone (26) and the second heat exchanger (39) link, so that the reaction gas stream (38) into the anode side of the oxygen transport membrane (80) within said reaction zone; the catalyst bed (28) positioned within the reaction zone (36), a combined partial oxidation - reforming - water gas shift reaction, to facilitate permeation of the oxygen reaction, thereby producing a synthesis gas product stream (40); and a first exhaust passage into the (68,7 4)与第一热交换器(20)联通,第二进入和排放通道(82,86)与第二热交换器联通(39),为含氧气流和贫氧气流(10,18)以及为反应气流和合成气产品气流(38,40)分别提供来往于反应器(72)的通道;和第一热交换器(20)、第二热交换器(39)、氧气传输膜(80)彼此相互独立地安装在反应器(72)中,以便能独立地进行膨胀或收缩。 4) a first heat exchanger (20) China Unicom, the second inlet and the discharge passage (82, 86) link the second heat exchanger (39), an oxygen-containing gas stream and an oxygen-depleted stream (10, 18) as well as the the reaction product gas stream and the syngas stream (38, 40) provide passage to and from the reactor (72); and (20), a second heat exchanger a first heat exchanger (39), the oxygen transport membrane (80) with each other independently of one another installed in a reactor (72) in order to independently expand or contract.
2.权利要求1的装置,其中氧气传输膜(80)由氧气传输膜管制成;惰性缓冲气体区(130)位于氧气传输膜(80)开口端的密封位置(126)和反应区域(26)之间,在大于反应区域(26)处的压力水平下,允许非反应性气体进入那里,以防止反应气体从反应气流(38)泄漏到含氧气流(10)中。 2. The device of claim, wherein the oxygen transmission membrane (80) is made of an oxygen transport membrane control; inert buffer gas zone (130) located in an oxygen transport membrane (80) end seal location (126) and a reaction zone openings (26) room, at a pressure level greater than the reaction zone (26) at, allowing non-reactive gas to enter there, in order to prevent leakage of reaction gas from the reaction gas stream (38) to the oxygen-containing gas stream (10).
3.权利要求1的装置,其中第一和第二热交换器(20,39)中的每一个都有一个与反应器(72)相连的热交换管板(116,114)和若干与所述管板相连的管道,它们分别作为所述合成气产品气流和所述含氧气流的通道。 3. The apparatus of claim 1, wherein each of which has a reactor (72) of the first and second heat exchangers (20, 39) in the heat exchange tubes connected to the plate (116, 114) and a number of the said duct is connected to the tube plate, respectively, as the passage of the syngas product stream and an oxygen-containing gas stream.
4.权利要求5的装置,其中所述氧气传输膜(80)为一端开口、另一端封闭的管状结构,由位于热交换器管板(116,114)之间的支撑管板(106)在它们所述的开口端处进行支撑。 4. The apparatus of claim 5, wherein the oxygen transmission membrane (80) is open at one end, the other end of the closed tubular structure, supported by a tube sheet (106) of the heat exchanger tube sheet (116, 114) between the said open end thereof is supported.
5.权利要求1的装置,其中反应器(72)有一个预热含氧气流(10)的外夹套(140)和一个在外夹套(140)和第一热交换器(20)之间联通的通道(140),含氧气流(10)预热后流过该通道(140)。 5. The apparatus of claim 1, wherein the reactor (72) there between (140) and an outer jacket (140) and a first heat exchanger (20) a preheated oxygen-containing gas stream (10) of the outer jacket Unicom channel (140), the oxygen-containing gas stream flowing through the passage (140) (10) preheating.
6.一种合成气的制备方法,包括:把含氧气流(10)压缩到约1.5巴到约4巴的压力范围内;加热所述含氧气流(10)到约300℃至约600℃之间的适中温度范围内;预热反应气流(38)至200℃以上的温度,其中反应气流(38)包括至少一种碳氢化合物、蒸汽和一种选自氢气、一氧化碳和二氧化碳的循环气;将加热以后的所述含氧气流(10)导入到位于反应器(72)内的第一热交换器(20)中,通过与贫氧气流(18)间接热交换来加热所述含氧气流(10);将所述反应气流(38)导入位于所述反应器(72)内的第二热交换器(39)中,通过与合成气产品气流(40)的间接热交换,将所述反应气流(38)加热到约500℃至约750℃之间的温度范围内;将所述含氧气流(10)导入位于反应器(72)的反应区域(26)内的若干氧气传输膜(80)的阴极一侧,把氧气从含氧气流(10)中分离出来,由此在氧气传输膜(80)的阳极一侧产生渗透 6. A method for preparing synthesis gas, comprising: the oxygen-containing gas stream (10) compressed to a pressure of about 1.5 bar to about 4 bar; heating the oxygen-containing gas stream (10) to about 300 deg.] C to about 600 ℃ within a medium temperature range between; preheated reactive gas stream (38) to above 200 ℃ temperature, wherein the reaction gas stream (38) comprising at least one hydrocarbon, steam, and one cycle gas selected from hydrogen, carbon monoxide and carbon dioxide ; the oxygen-containing gas stream (10) is heated after the first heat exchanger is introduced into (20) of the reactor (72) therein, to heat the oxygen-depleted oxygen-containing gas by stream (18) by indirect heat exchange stream (10); the reaction gas stream (38) introduced in the second heat exchanger (39) within the reactor (72), by indirect heat exchange with the synthesis gas product stream (40), the said reactive gas stream (38) heated to a temperature in the range between about 500 deg.] C to about 750 deg.] C; oxygen transmission film in a plurality of said oxygen-containing gas stream (10) introduced into the reaction zone of the reactor (72) (26) (80) the cathode side, the oxygen separation from oxygen-containing gas stream (10) out, thereby generating the permeate side of the oxygen transport membrane in the anode (80) ;将所述反应气流(30)导入位于所述氧气传输膜(80)阳极一侧(29)的催化剂床(28),并在反应区域(26)内,促进组合的部分氧化-重整-水煤气转换反应中的渗透氧的反应,产生合成气产品气流;通过和反应气流(38)的间接热交换被冷却后,从反应器(72)中回收合成气产品气流(40);通过和含氧气流(10)的间接热交换被冷却后,从所述反应器(72)中回收贫氧气流(18)。 ; The reaction gas stream (30) introduced into the oxygen transport membrane located (80) on the anode side (29) of the catalyst bed (28), and in the reaction zone (26), partial oxidation promoting composition - Reforming - water gas shift reaction permeate oxygen reaction to produce synthesis gas product stream; is cooled, recycled syngas product stream (40) from the reactor (72) by indirect heat and reactive gas stream (38) of the exchange; by containing after indirect hot oxygen stream (10) is cooled in the exchange, the recovery of oxygen-depleted stream (18) from said reactor (72).
7.权利要求6的方法,反应气流(38)中的反应气体,按照轴向流动、轴向横向混合流动、螺旋流动、径向分段交叉流动和横向分段交叉流动之一的方式,流经反应区域(26)并因此流经催化剂床(28)。 The reaction gases method of claim 6, the reaction gas stream (38) in accordance with axial flow, mixed flow axial lateral, spiral flow, radial flow of one embodiment of cross sections and cross sections transverse flow, stream reacted region (26) and thus through the catalyst bed (28).
8.权利要求6的方法,其中至少调节反应气体的组分、透过氧气传输膜(80)的渗透氧的氧气渗透速率、位于反应区域(26)内的用于促进反应气流(38)和渗透氧气反应的催化剂床(28)的催化剂活性的三者之一,使吸热的重整反应的热量与放热的氧化和水煤气转换反应的热量达到局部平衡,以保持所述氧气传输膜(80)的操作温度在800℃到1100℃之间。 The method of claim 6, wherein adjusting at least components of the reaction gas, an oxygen permeation rate of oxygen transmission through the film (80) permeation of oxygen, is located in the reaction zone for (26) to facilitate the reaction gas stream (38) and one of the three catalyst beds (28) of oxygen permeation of the reaction activity of the catalyst, and the heat of the endothermic reforming reaction of the exothermic oxidation and water gas shift reaction heat to achieve local equilibrium, to maintain the oxygen transmission membrane ( 80) operating at a temperature between 800 deg.] C to 1100 ℃.
9.权利要求6的方法,其中从所述产品第二热交换器(39)中出来的产品合成气气流(40)的排放温度保持在700℃以上,以抑制金属粉尘化,以及在反应器(72)外将产品合成气(40)在外部热交换器(46)内用沸水进一步冷却到400℃以下,以抑制所述外面热交换器(46)内的金属粉尘化。 9. The method as claimed in claim 6, the product synthesis gas stream (40) wherein the product from the second heat exchanger (39) out of the exhaust temperature is maintained at above 700 deg.] C, in order to suppress metal dusting, in reactor, and (72) outside the product syngas (40) in an external heat exchanger (46) is further cooled using boiling water to less 400 ℃, to inhibit metal in the outer heat exchanger (46) of the dust.
10.权利要求6的方法,其中液态水注入离开所述反应区域(26)后的产品合成气气流(40),通过淬灭来部分地冷却所述产品合成气流(40),由此抑制所述第二热交换器(39)内的金属粉尘化。 10. A method as claimed in claim 6, wherein the liquid injected into the product synthesis gas stream leaving (40) after the reaction zone (26) by quenching to partially cool the product synthesis gas stream (40), thereby inhibiting the metal in said second heat exchanger (39) of the dust.
CN 02819747 2001-08-10 2002-08-07 Ion transport membrane apparatus and process CN1564708A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US09/925,366 US20030039601A1 (en) 2001-08-10 2001-08-10 Oxygen ion transport membrane apparatus and process for use in syngas production

Publications (1)

Publication Number Publication Date
CN1564708A true CN1564708A (en) 2005-01-12

Family

ID=25451631

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 02819747 CN1564708A (en) 2001-08-10 2002-08-07 Ion transport membrane apparatus and process

Country Status (9)

Country Link
US (1) US20030039601A1 (en)
EP (1) EP1420877A4 (en)
JP (1) JP2004537487A (en)
CN (1) CN1564708A (en)
BR (1) BR0211845A (en)
CA (1) CA2456863A1 (en)
NO (1) NO20040546L (en)
WO (1) WO2003013716A1 (en)
ZA (1) ZA200400932B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102514701A (en) * 2011-12-07 2012-06-27 上海穗杉实业有限公司 System and method for guaranteeing oxygen supply on ship
CN103459010A (en) * 2011-02-18 2013-12-18 荷兰能源建设基金中心 Membrane reactor and process for the production of a gaseous product with such reactor
CN104121032A (en) * 2014-08-13 2014-10-29 中煤科工集团重庆研究院有限公司 Mining membrane type high-low pressure conversion device
CN105271128A (en) * 2015-11-23 2016-01-27 北京京诚泽宇能源环保工程技术有限公司 Ionic membrane oxygen generation system

Families Citing this family (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1477220A1 (en) * 2003-05-16 2004-11-17 Methanol Casale S.A. Chemical reactor
US7771519B2 (en) * 2005-01-03 2010-08-10 Air Products And Chemicals, Inc. Liners for ion transport membrane systems
US7425231B2 (en) 2003-08-06 2008-09-16 Air Products And Chemicals, Inc. Feed gas contaminant removal in ion transport membrane systems
US7658788B2 (en) 2003-08-06 2010-02-09 Air Products And Chemicals, Inc. Ion transport membrane module and vessel system with directed internal gas flow
US7179323B2 (en) * 2003-08-06 2007-02-20 Air Products And Chemicals, Inc. Ion transport membrane module and vessel system
US20050132648A1 (en) * 2003-11-27 2005-06-23 Kyocera Corporation Fuel reformer housing container and fuel reforming apparatus
US20050172554A1 (en) * 2004-02-10 2005-08-11 Kyocera Corporation Fuel reformer housing container and fuel reforming apparatus
US7419648B2 (en) * 2004-07-16 2008-09-02 Shell Oil Company Process for the production of hydrogen and carbon dioxide
US7556675B2 (en) * 2005-10-11 2009-07-07 Air Products And Chemicals, Inc. Feed gas contaminant control in ion transport membrane systems
DE102005060171A1 (en) * 2005-12-14 2007-06-21 Borsig Process Heat Exchanger Gmbh Oxidation reactor and oxidation process
FR2898518B1 (en) * 2006-03-17 2009-01-16 Inst Francais Du Petrole Internal combustion heat exchanger reactor for endothermic reaction in fixed bed
CA2659278A1 (en) * 2006-07-28 2008-01-31 William S. Rollins Iii High efficiency integrated gasification combined cycle power plant
US20080155984A1 (en) * 2007-01-03 2008-07-03 Ke Liu Reforming system for combined cycle plant with partial CO2 capture
US8356485B2 (en) * 2007-02-27 2013-01-22 Siemens Energy, Inc. System and method for oxygen separation in an integrated gasification combined cycle system
US8262755B2 (en) 2007-06-05 2012-09-11 Air Products And Chemicals, Inc. Staged membrane oxidation reactor system
US8237000B2 (en) 2008-06-19 2012-08-07 Lummus Technology, Inc. Combined carbon dioxide and oxygen process for ethylbenzene dehydrogenation to styrene
EP2147896A1 (en) * 2008-07-22 2010-01-27 Uhde GmbH Low energy process for the production of ammonia or methanol
US9561476B2 (en) 2010-12-15 2017-02-07 Praxair Technology, Inc. Catalyst containing oxygen transport membrane
US8287762B2 (en) 2010-04-02 2012-10-16 Air Products And Chemicals, Inc. Operation of staged membrane oxidation reactor systems
CN103987681B (en) 2011-12-15 2016-08-24 普莱克斯技术有限公司 Oxygen transport membrane composite
US9486735B2 (en) 2011-12-15 2016-11-08 Praxair Technology, Inc. Composite oxygen transport membrane
JP2016505501A (en) 2012-12-19 2016-02-25 プラクスエア・テクノロジー・インコーポレイテッド Method for sealing an oxygen transport membrane assembly
US9453644B2 (en) 2012-12-28 2016-09-27 Praxair Technology, Inc. Oxygen transport membrane based advanced power cycle with low pressure synthesis gas slip stream
US9212113B2 (en) * 2013-04-26 2015-12-15 Praxair Technology, Inc. Method and system for producing a synthesis gas using an oxygen transport membrane based reforming system with secondary reforming and auxiliary heat source
US9023245B2 (en) * 2013-04-26 2015-05-05 Praxair Technology, Inc. Method and system for producing a synthesis gas using an oxygen transport membrane based reforming system with secondary reforming
US9611144B2 (en) * 2013-04-26 2017-04-04 Praxair Technology, Inc. Method and system for producing a synthesis gas in an oxygen transport membrane based reforming system that is free of metal dusting corrosion
US9296671B2 (en) 2013-04-26 2016-03-29 Praxair Technology, Inc. Method and system for producing methanol using an integrated oxygen transport membrane based reforming system
US9938145B2 (en) 2013-04-26 2018-04-10 Praxair Technology, Inc. Method and system for adjusting synthesis gas module in an oxygen transport membrane based reforming system
US9365422B2 (en) 2013-04-26 2016-06-14 Praxair Technology, Inc. Method and system for producing a synthesis gas in an oxygen transport membrane based reforming system with recycling of the produced synthesis gas
WO2015054219A2 (en) 2013-10-07 2015-04-16 Praxair Technology, Inc. Ceramic oxygen transport membrane array reactor and reforming method
BR112016007641A2 (en) 2013-10-08 2017-08-01 Praxair Technology Inc method for temperature control in a reactor, and reactor
US9556027B2 (en) 2013-12-02 2017-01-31 Praxair Technology, Inc. Method and system for producing hydrogen using an oxygen transport membrane based reforming system with secondary reforming
US9562472B2 (en) 2014-02-12 2017-02-07 Praxair Technology, Inc. Oxygen transport membrane reactor based method and system for generating electric power
US9028720B1 (en) 2014-03-05 2015-05-12 Air Products And Chemicals, Inc. Ion transport membrane reactor systems and methods for producing synthesis gas
US9789445B2 (en) 2014-10-07 2017-10-17 Praxair Technology, Inc. Composite oxygen ion transport membrane
US10441922B2 (en) 2015-06-29 2019-10-15 Praxair Technology, Inc. Dual function composite oxygen transport membrane
US10118823B2 (en) 2015-12-15 2018-11-06 Praxair Technology, Inc. Method of thermally-stabilizing an oxygen transport membrane-based reforming system
US9938146B2 (en) 2015-12-28 2018-04-10 Praxair Technology, Inc. High aspect ratio catalytic reactor and catalyst inserts therefor

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1141102B (en) * 1980-11-28 1986-10-01 Ammonia Casale Sa axial-radial reactor for heterogeneous synthesis
DK167242B1 (en) * 1989-02-16 1993-09-27 Topsoe Haldor As Apparatus and method for exothermic reactions
US5342431A (en) * 1989-10-23 1994-08-30 Wisconsin Alumni Research Foundation Metal oxide membranes for gas separation
US5567398A (en) * 1990-04-03 1996-10-22 The Standard Oil Company Endothermic reaction apparatus and method
US5160713A (en) * 1990-10-09 1992-11-03 The Standard Oil Company Process for separating oxygen from an oxygen-containing gas by using a bi-containing mixed metal oxide membrane
US6033632A (en) * 1993-12-08 2000-03-07 Eltron Research, Inc. Solid state oxygen anion and electron mediating membrane and catalytic membrane reactors containing them
AU706663B2 (en) * 1994-09-23 1999-06-17 Standard Oil Company, The Oxygen permeable mixed conductor membranes
US5567933A (en) * 1995-02-14 1996-10-22 Mason & Hanger National, Inc. Optical fiber detection system with disturbance and positive cut-loop detection capabilities
US5599383A (en) * 1995-03-13 1997-02-04 Air Products And Chemicals, Inc. Tubular solid-state membrane module
US5681373A (en) * 1995-03-13 1997-10-28 Air Products And Chemicals, Inc. Planar solid-state membrane module
KR100275822B1 (en) * 1995-05-18 2000-12-15 조안 엠. 젤사 Pressure driven solid electrolyte membrane gas separation method
US5775414A (en) * 1996-06-13 1998-07-07 Graham; Robert G. High temperature high pressure air-to-air heat exchangers and assemblies useful therein
US5733069A (en) * 1996-11-21 1998-03-31 Schofield, Jr.; John P. Loose roof plate retensioning device
US5980840A (en) * 1997-04-25 1999-11-09 Bp Amoco Corporation Autothermic reactor and process using oxygen ion--conducting dense ceramic membrane
US5820654A (en) * 1997-04-29 1998-10-13 Praxair Technology, Inc. Integrated solid electrolyte ionic conductor separator-cooler
US5865878A (en) * 1997-04-29 1999-02-02 Praxair Technology, Inc. Method for producing oxidized product and generating power using a solid electrolyte membrane integrated with a gas turbine
US5820655A (en) * 1997-04-29 1998-10-13 Praxair Technology, Inc. Solid Electrolyte ionic conductor reactor design
ID20211A (en) * 1997-04-29 1998-10-29 Praxair Technology Inc Hydrogen production method using the solid electrolyte membrane
US6077323A (en) * 1997-06-06 2000-06-20 Air Products And Chemicals, Inc. Synthesis gas production by ion transport membranes
US5954859A (en) * 1997-11-18 1999-09-21 Praxair Technology, Inc. Solid electrolyte ionic conductor oxygen production with power generation
US6048472A (en) * 1997-12-23 2000-04-11 Air Products And Chemicals, Inc. Production of synthesis gas by mixed conducting membranes
US6153163A (en) * 1998-06-03 2000-11-28 Praxair Technology, Inc. Ceramic membrane reformer
US6139810A (en) * 1998-06-03 2000-10-31 Praxair Technology, Inc. Tube and shell reactor with oxygen selective ion transport ceramic reaction tubes
US6394043B1 (en) * 2000-12-19 2002-05-28 Praxair Technology, Inc. Oxygen separation and combustion apparatus and method

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103459010A (en) * 2011-02-18 2013-12-18 荷兰能源建设基金中心 Membrane reactor and process for the production of a gaseous product with such reactor
CN103459010B (en) * 2011-02-18 2015-12-23 荷兰能源建设基金中心 Membrane reactor and method for producing gaseous product by the reactor
CN102514701A (en) * 2011-12-07 2012-06-27 上海穗杉实业有限公司 System and method for guaranteeing oxygen supply on ship
CN102514701B (en) 2011-12-07 2014-02-19 中国舰船研究设计中心 System and method for guaranteeing oxygen supply on ship
CN104121032A (en) * 2014-08-13 2014-10-29 中煤科工集团重庆研究院有限公司 Mining membrane type high-low pressure conversion device
CN104121032B (en) * 2014-08-13 2016-03-02 中煤科工集团重庆研究院有限公司 Mine high and low voltage thin film switching means
CN105271128A (en) * 2015-11-23 2016-01-27 北京京诚泽宇能源环保工程技术有限公司 Ionic membrane oxygen generation system

Also Published As

Publication number Publication date
ZA200400932B (en) 2004-10-18
US20030039601A1 (en) 2003-02-27
NO20040546L (en) 2004-04-06
WO2003013716A1 (en) 2003-02-20
JP2004537487A (en) 2004-12-16
CA2456863A1 (en) 2003-02-20
BR0211845A (en) 2006-04-04
EP1420877A1 (en) 2004-05-26
EP1420877A4 (en) 2006-05-24

Similar Documents

Publication Publication Date Title
DE60106737T2 (en) Method for producing hydrogen-substituted metal-membrane modules
CA2273625C (en) Syngas reactor and ceramic membrane
US8262755B2 (en) Staged membrane oxidation reactor system
US4690690A (en) Steam reforming hydrocarbons
US6783741B2 (en) Fuel processing system
JP4745219B2 (en) Self-thermal reformer for hydrogen production-reformer exchanger arrangement
AU728728B2 (en) Synthesis gas production by steam reforming using catalyzed hardware
US6623719B2 (en) System for hydrogen generation through steam reforming of hydrocarbons and integrated chemical reactor for hydrogen production from hydrocarbons
CA1328558C (en) Reactor for reforming hydrocarbon and process for reforming hydrocarbon
US5167933A (en) Heat exchange reforming process and reactor system
US6190623B1 (en) Apparatus for providing a pure hydrogen stream for use with fuel cells
EP1094030B1 (en) Reforming method and apparatus for hydrogen production
FI119624B (en) Endothermic reaction apparatus
US7217303B2 (en) Pressure swing reforming for fuel cell systems
US6162267A (en) Process for the generation of pure hydrogen for use with fuel cells
CA1308256C (en) Vessel for the generation of synthesis gas
US20080038598A1 (en) Fuel cell fuel processor with hydrogen buffering and staged membrane
US6461408B2 (en) Hydrogen generator
US6280864B1 (en) Control system for providing hydrogen for use with fuel cells
CN100457252C (en) Compact steam reformer
CA2529082C (en) Fuel conversion reactor
US20040126288A1 (en) Hydrogen generator for fuel cell
JP2007523042A (en) Integrated fuel processor for distributed hydrogen production
US6821501B2 (en) Integrated flameless distributed combustion/steam reforming membrane reactor for hydrogen production and use thereof in zero emissions hybrid power system
US4315893A (en) Reformer employing finned heat pipes

Legal Events

Date Code Title Description
C06 Publication
C10 Request of examination as to substance
C02 Deemed withdrawal of patent application after publication (patent law 2001)